KR102041928B1 - Negative-type photosensitive resin composition - Google Patents
Negative-type photosensitive resin composition Download PDFInfo
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- KR102041928B1 KR102041928B1 KR1020150165229A KR20150165229A KR102041928B1 KR 102041928 B1 KR102041928 B1 KR 102041928B1 KR 1020150165229 A KR1020150165229 A KR 1020150165229A KR 20150165229 A KR20150165229 A KR 20150165229A KR 102041928 B1 KR102041928 B1 KR 102041928B1
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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
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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Abstract
The present invention relates to a negative photosensitive resin composition, more specifically, an alkali-soluble resin including repeating units represented by specific formulas; A polymerizable compound including a compound represented by a specific formula; Photopolymerization initiator; And a solvent; developability can be improved.
Description
The present invention relates to a negative photosensitive resin composition.
In the field of display, the photosensitive resin composition is used to form various photocuring patterns such as photoresist, insulating film, protective film, black matrix, column spacer and the like. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocuring pattern. In this process, the photosensitive resin having high sensitivity is used to improve the yield of the process and to improve the physical properties of the application target. A composition is required.
On the other hand, general display devices have used silica beads or plastic beads having a constant diameter in order to maintain a constant distance between the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and positioned inside the pixel, the aperture ratio is lowered and light leakage occurs. In order to solve these problems, a spacer formed by photolithography is started to be used inside a display device. Currently, spacers used in most display devices are formed by photolithography.
The method of forming a spacer by photolithography is to apply a photosensitive resin composition on a substrate, irradiate ultraviolet rays through a mask, and then form the spacer at a desired position on the substrate according to a pattern formed on the mask through a developing process.
In general, the photocuring composition for photoresist after photocrosslinking is subjected to a development process, and the structure is developed by using TMAH (Tetramethylammonium Hydroxide) solution or KOH (Potassium Hydroxide) solution depending on the purpose of the photoresist. Form. This development process plays a very important role in forming the size (depth, height, width, etc.) of the structure formed after development.
As the size of the structure (depth, height, width, etc.) is precisely formed, the developability of the photoresist may be improved, which may depend on physical and optical techniques in the process, such as narrowing the line width.
Accordingly, Korean Patent No. 10-1359470 includes alkali-soluble resins, photocurable monomers, photopolymerization initiators, aminoacetophenone-based or aminobenzaldehyde-based hydrogen donors and solvents as photosensitive resin compositions, thereby improving photoreactivity and light efficiency and developing properties. It discloses a technique to improve the.
However, there may be limitations in terms of improving developability.
An object of the present invention is to provide a photosensitive resin composition which is excellent in sensitivity and reactivity and excellent in sensibility.
The present invention can increase the developability of the photocured composition to obtain a narrower line width.
Moreover, an object of this invention is to provide the photocuring pattern formed from the said photosensitive resin composition, and the image display apparatus containing the same.
1. Alkali-soluble first resin containing a repeating unit represented by following formula (1);
An alkali-soluble second resin including a repeating unit represented by Formula 2 below;
A polymerizable compound including a compound represented by Formula 3 below;
Photopolymerization initiator; And
A negative photosensitive resin composition comprising a solvent:
[Formula 1]
[Formula 2]
(Wherein, R 1 ′ is a hydrogen atom or a methyl group, R 2 ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 ′ is a hydrogen atom or a methyl group.
[Formula 3]
(In the formula,
R 31 is carbon or a saturated hydrocarbon group having 2 to 6 carbon atoms,
R 32 is independently of each other hydrogen, acryloyloxy group, succinate group or a straight or branched chain alkyl group having 1 to 5 carbon atoms,
n is an integer from 3 to 8,
The molecule represented by Formula 3 includes at least two acryloyloxy groups.
2. In the above 1, wherein the first resin is represented by the following formula 1-1, negative photosensitive resin composition:
[Formula 1-1]
(Wherein R 4 , R 5 , R 6 and R 7 are each independently hydrogen or a methyl group,
R 8 is benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl) phenol propyl (meth) acrylate, 2-hydroxy- (3-phenyl) phenoxy propyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) styrene, vinyltoluene, vinyl Naphthalene, N-benzylmaleimide, methyl (meth) acrylate, ethyl (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth Acrylate, methoxy tetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) acrylate The structure derived from the monomer selected from the group,
R 9 is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7),
R 10 is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- It is a structure derived from the monomer chosen from the group which consists of (meth) acryloyloxyethyl succinate,
R 11 is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol%, d = 5 to 30-> 50 mol%).
3. In the above 1, wherein the first resin is represented by the following formula 2-1, negative photosensitive resin composition:
[Formula 2-1]
(Wherein R 16 and R 17 are each independently hydrogen or a methyl group,
R 18 is a structure derived from a monomer selected from the group consisting of the following formula (8),
Wherein R a is a single bond or alkylene having 1 to 6 carbon atoms, and the alkylene may further include an oxygen atom.
R 19 is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- A structure derived from a monomer selected from the group consisting of (meth) acryloyloxyethyl succinate,
e = 40 to 95 mol%, f = 5 to 60 mol%).
4. In the above 1, wherein the compound represented by Formula 3 is a compound represented by the following formula 4 or 5, the negative photosensitive resin composition:
[Formula 4]
[Formula 5]
5. In the above 1, wherein the photopolymerization initiator is at least one of the biimidazole-based and oxime ester-based, negative photosensitive resin composition.
6. Photocuring pattern made of the negative photosensitive resin composition according to any one of the above 1 to 5.
7. In the above 6, the photocuring pattern is selected from the group consisting of adhesive layer, array planarization film pattern, protective film pattern, insulating film pattern, photoresist pattern, color filter pattern, black matrix pattern and column spacer pattern, photocuring pattern.
8. Image display device having a photocuring pattern of the above six.
The photosensitive resin composition of the present invention is excellent in sensitivity and reactivity, and the pattern prepared therefrom exhibits excellent adhesion to the substrate and excellent mechanical properties.
The present invention can increase the developability of the photocured composition to obtain a narrower line width.
Since the photocurable pattern made of the photosensitive resin composition of the present invention may be formed in a fine pattern, high resolution may be realized when applied to a product.
One embodiment of the present invention is an alkali-soluble first resin comprising a repeating unit represented by the following formula (1); An alkali-soluble second resin including a repeating unit represented by Formula 2 below; A polymerizable compound including a compound represented by Formula 3 below; Photopolymerization initiator; And a solvent; relates to a negative photosensitive resin composition excellent in developability.
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, this is only an example and the present invention is not limited thereto.
< Negative Photosensitive Resin Composition>
The negative photosensitive resin composition of this invention is alkali-soluble 1st resin containing the repeating unit represented by following General formula (1); An alkali-soluble second resin including a repeating unit represented by Formula 2 below; A polymerizable compound including a compound represented by Formula 3 below; Photopolymerization initiator; And solvents.
In the present invention, when the repeating unit, compound or resin represented by each formula contains an isomer of a repeating unit, compound or resin represented by the formula, the repeating unit, compound or Resin means a representative chemical formula including the isomer thereof.
In the present invention, "(meth) acryl-" refers to "methacryl-", "acryl-" or both.
Alkali soluble resin
Alkali-soluble resin (A) used for this invention is a component which provides solubility to the alkaline developing solution used at the image development process at the time of forming a pattern, The 1st resin containing the repeating unit represented by following General formula (1), and It includes a second resin containing a repeating unit represented by the formula (2).
[Formula 1]
[Formula 2]
(Wherein, R 1 ′ is a hydrogen atom or a methyl group, R 2 ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 ′ is a hydrogen atom or a methyl group.
< First resin >
The first resin according to the present invention is not particularly limited as long as it includes a repeating unit represented by Formula 1, and may include, for example, a repeating unit represented by Formula 1-1.
[Formula 1-1]
(Wherein R 4 , R 5 , R 6 and R 7 are each independently hydrogen or a methyl group,
R 8 is benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl) phenol propyl (meth) acrylate, 2-hydroxy- (3-phenyl) phenoxy propyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) styrene, vinyltoluene, vinyl Naphthalene, N-benzylmaleimide, methyl (meth) acrylate, ethyl (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth Acrylate, methoxy tetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) acrylate The structure derived from the monomer selected from the group,
R 9 is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7),
R 10 is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- It is a structure derived from the monomer chosen from the group which consists of (meth) acryloyloxyethyl succinate,
R 11 is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol%, d = 5 to 50 mol%).
Preferred examples of the repeating unit represented by Formula 1-1 according to the present invention include repeating units represented by the following Formula 1-2.
[Formula 1-2]
(Wherein R 12 , R 13 , R 14 and R 15 are each independently hydrogen or a methyl group, a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol%, d = 5 to 50 mol %).
It is preferable that the weight average molecular weights of a 1st resin are 10,000-30,000 from the point of showing the best pattern formation property and developability. It can exhibit the most excellent pattern formation, developability in the above molecular weight range.
< Second resin >
Since the second resin according to the present invention includes a repeating unit represented by Chemical Formula 2, the thermosetting reaction occurs through the ring-opening polymerization reaction of the epoxy functional group and the carboxylic acid in the post-bait step, and thus formed as the negative photosensitive resin composition of the present invention. The pattern can be more firmly formed through radical polymerization of the first resin and thermosetting reaction of the second resin.
The second resin according to the present invention is not particularly limited as long as it includes a repeating unit represented by Formula 2, and may include, for example, a repeating unit represented by the following Formula 2-1.
[Formula 2-1]
(Wherein R 16 and R 17 are each independently hydrogen or a methyl group,
R 18 is a structure derived from a monomer of the following formula (8),
Wherein R a is a single bond or alkylene having 1 to 6 carbon atoms, and the alkylene may further include an oxygen atom.
R 19 is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- A structure derived from a monomer selected from the group consisting of (meth) acryloyloxyethyl succinate,
e = 40 to 95 mol%, f = 5 to 60 mol%).
In addition, preferred examples of the compound of formula 2-1 according to the present invention include a compound of formula 2-2.
[Formula 2-2]
(Wherein R 16 and R 17 are each independently hydrogen or a methyl group, e = 50 to 95 mol%, f = 5 to 50 mol%).
In view of further improving the adhesion, the weight average molecular weight of the second resin is preferably 2,000 to 20,000.
In the present invention, each repeating unit represented by the formulas (1) to (2) and (1-1) to (2-2) is construed as limited to those represented by formulas (1) to (2) and (1-1) to (2-2) No, the sub repeat units in parentheses may be freely positioned at any position in the chain within the specified mole percent range. That is, the parentheses of the formulas (1) to (2) and (1-1) to (2-2) are represented by one block to express mole%, but each sub-repeat unit is separated into blocks or separately without limitation if it is in the resin Can be positioned.
If necessary, the first resin and the second resin according to the present invention may further include a repeating unit formed of other monomers known in the art, in addition to the repeating units of Formulas 1-1 and 2-1 independently of each other, It may be formed only of the repeating units of the formula (2-1) and (2-1).
Although it does not specifically limit as a monomer which forms the repeating unit which can be added further to general formula (1-1) and general formula (2-1), For example, Monocarboxylic acids, such as crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid and anhydrides thereof; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate; Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate; Alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and 2-dicyclopentanyloxyethyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds; Unsaturated oxirane compounds such as methylglycidyl (meth) acrylate; (Meth) acrylate substituted with a cycloalkane or dicycloalkane ring having 4 to 16 carbon atoms; Etc. can be mentioned. These can be used individually or in mixture of 2 or more types.
In the alkali-soluble resin according to the present invention, when the first resin including the repeating unit of Formula 1 and the second resin including the repeating unit of Formula 2 are used simultaneously, the mixing weight ratio is 20:80 to 80:20 days. It may be, preferably from 30:70 to 70:30. It may exhibit the best adhesion, developability, T / B ratio in the above range.
It is preferable that alkali-soluble resin has an acid value of 20-200 (KOHmg / g). If the acid value is in the above range, it may have excellent developability and stability over time.
The content of the alkali-soluble resin is not particularly limited, for example, it may be included in 10 to 80 parts by weight, preferably 20 to 60 parts by weight based on 100 parts by weight of the total composition solids. When included in the above range, the solubility in the developing solution is sufficient to improve the developability, good adhesion to the lower substrate and excellent mechanical properties and to form a photocuring pattern of narrow line width.
Polymerizable compound
The polymerizable compound used in the negative photosensitive resin composition of the present invention can increase the crosslinking density during the manufacturing process and can enhance the mechanical properties of the photocured pattern.
The polymerizable compound of the present invention is a compound represented by the following Chemical Formula 3:
[Formula 3]
(In the formula,
R 31 is carbon or a saturated hydrocarbon group having 2 to 6 carbon atoms,
R 32 is independently of each other hydrogen, acryloyloxy group, succinate group or a straight or branched chain alkyl group having 1 to 5 carbon atoms,
n is an integer from 3 to 8,
The molecule represented by Formula 3 includes at least two acryloyloxy groups.
Specifically, R 32 is a functional group of any one of hydrogen, an acryloyloxy group, a succinate group or a linear or branched alkyl group having 1 to 5 carbon atoms bonded to R 31 via a methylene group (—CH 2 —) N may be included in Formula 3, and each of the n functional groups may be independently selected from hydrogen, acryloyloxy group, succinate group, or a linear or branched alkyl group having 1 to 5 carbon atoms. have.
Meanwhile, R 31 may be, for example, one carbon element or the following Chemical Formula 3-1:
[Formula 3-1]
In which "*" represents a bond.
Also, preferably, the compound represented by Chemical Formula 3 may be a compound represented by the following Chemical Formula 4 or 5:
[Formula 4]
[Formula 5]
The content of the polymerizable compound is not particularly limited, but may be included, for example, 30 to 80 parts by weight, and preferably 40 to 60 parts by weight, based on 100 parts by weight of the total composition solids.
In addition, in another aspect of the present invention, the polymerizable compound may be included in an amount of 70 to 150 parts by weight based on 100 parts by weight of the total alkali-soluble resin, based on the solid content.
When the polymerizable compound is included in the above content range, the adhesion to the lower substrate is good, can have excellent durability, and can improve the developability of the composition.
By including a plurality of reactors that act as a crosslinking, it is considered that the developability can be increased to obtain a narrower line width.
Further usable polymerizable compounds may be used without particular limitation as used in the art, for example, monofunctional monomers, bifunctional monomers and other polyfunctional monomers, and the kind thereof is not particularly limited, Examples are compounds.
Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc. 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, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.
Photopolymerization Initiator
The photopolymerization initiator usable in the present invention can be used without particular limitation as long as it is a compound capable of polymerizing the polymerizable compound. For example, a group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound One or more compounds selected from may be used, and preferably, at least one of a biimidazole compound and an oxime compound may be used.
The negative photosensitive resin composition containing the photoinitiator is highly sensitive, and the strength and surface smoothness of the spacer pattern formed using the composition can be improved.
As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.
As said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.
Moreover, as said acetophenone type compound, the compound represented by following formula (6) is mentioned, for example.
[Formula 6]
In Formula 6, R 25 to R 28 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.
Specific examples of the compound represented by Formula 6 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .
As said biimidazole compound, the compound represented by following formula (7), 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'- tetraphenyl- 1,2'- Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, wherein the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group And imidazole compounds. Preferably, the compound represented by the following formula (7), 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetra phenylbiimidazole, 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2 At least one selected from the group consisting of '-biimidazole:
[Formula 7]
The oxime compound is o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, 1,2-octanedione, -1- (4-phenylthio) phenyl, -2- (o- Benzoyl oxime), ethanone, -1- (9-ethyl) -6- (2-methylbenzoyl-3-yl)-, 1- (o-acetyloxime), the following chemical formulas 8, 9, 10 and 10 It may be at least one selected from the group consisting of 11, preferably a compound represented by the following formula (8), o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione , -1- (4-phenylthio) phenyl, -2- (o-benzoyloxime) and ethanone, -1- (9-ethyl) -6- (2-methylbenzoyl-3-yl)-, 1- (o-acetyloxime) can be at least one selected from the group consisting of:
[Formula 8]
[Formula 9]
[Formula 10]
[Formula 11]
Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.
As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.
As said benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.
As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.
Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.
In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenyloxyoxylate, A titanocene compound etc. are mentioned as another photoinitiator.
Moreover, you may use the photoinitiator which has group which can cause chain transfer as a photoinitiator. As such a photoinitiator, what was described in Unexamined-Japanese-Patent No. 2002-544205 is mentioned, for example.
As a photoinitiator which has group which can cause said chain transfer, the compound represented by following formula (12) -17 is mentioned, for example.
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
[Formula 16]
[Formula 17]
In addition, in this invention, you may use combining a photoinitiator as a photoinitiator. When a photoinitiation adjuvant is used together with the said photoinitiator, since the negative photosensitive resin composition containing these becomes more sensitive and can improve productivity at the time of spacer formation, it is preferable.
As the photopolymerization start adjuvant, an amine compound and a carboxylic acid compound are preferably used.
Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid isoamyl. , 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4 ' Aromatic amine compounds, such as -bis (diethylamino) benzophenone, are mentioned. Among them, an aromatic amine compound is preferably used as the amine compound.
Specific examples of the carboxylic acid compound in the photopolymerization start adjuvant include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid and chlorophenyl And aromatic heteroacetic acids such as thioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.
The content of the photoinitiator is not particularly limited, but, for example, it may be included in 0.1 to 10 parts by weight, preferably 0.5 to 7, based on 100 parts by weight of the total composition solids. When the said range is satisfied, since a negative photosensitive resin composition becomes high sensitivity and the strength and smoothness of the spacer formed using this composition become favorable, it is preferable.
menstruum
The solvent can be used without any limitation as long as it is conventionally used in the art.
Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyl diol monoalkyl ethers such as methoxy butyl alcohol, ethoxy butyl alcohol, propoxy butyl alcohol and butoxy butyl alcohol; Butanediol monoalkyl ether acetates such as methoxy butyl acetate, ethoxy butyl acetate, propoxy butyl acetate and butoxy butyl acetate; Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate and butoxybutyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy 3-Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. The solvent illustrated here can be used individually or in mixture of 2 or more types, respectively.
The solvents include esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate in consideration of coating properties and drying properties. May be preferably used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl, diethylene glycol methylethyl ether and the like may be used alone or in combination of two or more thereof.
The content of the solvent may be included in an amount of 60 to 1900 parts by weight, preferably 80 to 600 parts by weight, based on 100 parts by weight of the total composition solids. When the content of the solvent is in the above range, it is preferable because the applicability becomes good when applied with a coating device such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), or an inkjet. Do.
additive
The negative photosensitive resin composition according to the present invention may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and chain transfer agents as necessary.
Specific examples of the filler include glass, silica, alumina and the like.
Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned.
Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.
The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.
As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.
As said leveling agent, commercially available surfactants can be used, For example, surfactants, such as a silicone type, a fluorine type, ester type, a cation type, an anion type, a nonionic type, an amphoteric, etc., are mentioned, These are each independently, either You may use in combination of 2 or more type.
As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoi Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), MegaPac (Dainippon Ink Chemical Co., Ltd.) Co., Ltd., Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahigard, Saffron (above, Asahigarasu Co., Ltd.), Soapaspa (Geneka Co., Ltd.), EFKA (EFKA CHEMICALS Co., Ltd.) Manufacture), PB821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.
As said adhesion promoter, a silane type compound is preferable, Specifically, a vinyl trimethoxysilane, a vinyl triethoxysilane, a vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.
Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) prop Foxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis ( 6-tert-butyl-4-methylphenol),
4,4 '-(butane-1,1-diyl) bis (2- (tert-butyl) -5-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methyl Phenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'- Thiodipropionate, dimyristyl 3,3'- thiodipropionate, distearyl 3,3'- thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate) , 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione , 3,3 ', 3' ', 5,5', 5 ''-hexa-tert-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p -Cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like Can be. Preferably 4,4 '-(butane-1,1-diyl) bis (2- (tert-butyl) -5-methylphenol).
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
As said aggregation inhibitor, sodium polyacrylate etc. are mentioned specifically ,.
Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.
The content of the additive may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition solids.
< Photocuring Pattern and Image Display Device>
An object of the present invention is to provide a photocuring pattern made of the negative photosensitive resin composition and an image display device including the photocuring pattern.
The photocuring pattern made of the negative photosensitive resin composition is capable of CD-Bias control and is excellent in T / B ratio value, developability, adhesion and mechanical properties. Accordingly, the image display device may be used as various patterns, for example, an adhesive layer, an array planarization film, a protective film, an insulating film pattern, or the like, and may be used as a photoresist, a black matrix, a column spacer pattern, and the like. In particular, it is very suitable as a spacer pattern.
An image display device having such a photocuring pattern or using the pattern during a manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto. All image display devices known in the art may be applied. Can be illustrated.
The manufacturing method of the photocuring pattern which concerns on this invention will not be specifically limited if it is a method known in the art, For example, the negative photosensitive resin composition of this invention mentioned above is apply | coated on a base material, and (development process as needed) After rough) can be produced by forming a photocured pattern.
First, after apply | coating a negative photosensitive resin composition to a board | substrate, it heat-drys, removes volatile components, such as a solvent, and obtains a smooth coating film.
As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying (prebaking) or drying under reduced pressure are carried out to volatilize volatile components such as a solvent. Here, heating temperature is 70-100 degreeC which is relatively low temperature. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.
G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation amount of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. The desired pattern shape can be formed by making the coating film after hardening contact with a developing solution as needed, melt | dissolving, and developing a non-exposed part.
The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.
These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.
The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.
Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.
The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After image development, it washes with water and performs post-baking for 10 to 60 minutes at 100-150 degreeC which is relatively low temperature.
Hereinafter, preferred examples are provided to help understanding of the present invention, but these examples are only for exemplifying the present invention, and do not limit the appended claims, but are within the scope and spirit of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
Production Example
Production Example 1. Synthesis of alkali-soluble resin (first resin (A-1))
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 g of propylene glycol monomethyl ether acetate was introduced, and the temperature was raised to 100 ° C., followed by 47.3 g of methacrylic acid ( 0.55 mole), 2,2'-azobis (2) in a mixture comprising 61.6 g (0.35 mole) benzyl methacrylate, 22.0 g (0.10 mole) tricyclodecanyl methacrylate and 150 g propylene glycol monomethylether acetate The solution to which 3.6 g of (4-dimethylvaleronitrile) was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours.
Subsequently, the atmosphere in the flask was changed from nitrogen to air, 42.6 g [0.30 mol (55 mol% of acrylic acid used in the reaction)] glycidyl methacrylate was added to the flask, and the reaction was continued at 110 DEG C for 6 hours. And unsaturated group containing resin A-1 whose solid acid value was 109 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 25,000, and molecular weight distribution (Mw / Mn) was 2.4.
Production Example 2. Synthesis of alkali-soluble resin (second resin (A-2))
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methylethyl ether was added and heated to 70 ° C while stirring. Next, a solution was prepared by dissolving 210.2 g (0.95 mol) and 14.5 g (0.17 mol) of methacrylic acid in 150 g of diethylene glycol methylethyl ether.
[Formula a]
The prepared solution was added dropwise into the flask using a dropping funnel, and then 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methylethyl ether. The dissolved solution was dropped into the flask over 4 hours using a separate dropping funnel. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer of 41.6 mass% of solid content and acid value of 65 mg-KOH / g (solid content equivalent) (A-2 ) Solution.
The weight average molecular weight Mw of obtained resin formula 2-3 was 8,300, and molecular weight distribution was 1.85.
Production Example 3. Synthesis of alkali-soluble resin (third resin (A-3))
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 g of diethylene glycol methylethyl ether acetate was introduced, and the temperature was raised to 100 ° C., and then 10.4 g (0.10 mol) ), 55.1 g (0.25 mol) of tricyclodecanyl acrylate, 12.9 g (0.15 mol) of methacrylic acid, and 71.1 g (0.50 mol) of glycidyl methacrylate were added, followed by 2,2'-azobis ( A solution of 2.0 g of 2,4-dimethylvaleronitrile) dissolved in 100 g of diethylene glycol methylethyl ether was added dropwise to the flask over 2 hours from the dropping lot, followed by further stirring at 100 ° C for 5 hours.
After completion of the reaction, an alkali-soluble resin A-3 having a solid acid value of 55 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 23,500, and molecular weight distribution (Mw / Mn) was 2.3.
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 Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, and the detector RI was used. The measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), a calibration standard. The material used was TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation).
The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).
Example And Comparative example
The photosensitive resin composition which has the composition and content (weight part) of following Table 1, Table 2, and Table 3 was prepared.
(A)
(C)
(A)
(C)
A-1: alkali-soluble resin represented by [Formula 1-3]
A-2: Cyclopentin oxide functional group represented by [Formula 2-3]
Including thermosetting resin
A-3: Thermosetting resin represented by [Formula 2-4]
B-1: The tetrafunctional polymeric compound represented by [Formula 4]
B-2: 6-functional polymerizable compound represented by [Formula 5]
B-3: Polyfunctional polymerizable compound represented by [Formula 18]
B-4: The polyfunctional polymerizable compound represented by [Formula 19].
C-1: photoinitiator represented by [Formula 6]
C-2: photoinitiator represented by [Formula 7]
E: compound of Formula 20
F-1: diethylene glycol methylethyl ether
F-2: Propylene Glycol Monomethyl Ether Acetate
[Formula 1-3]
[Formula 2-3]
(e = 50 mol%, f = 50 mol%)
[Formula 2-4]
(a = 10 mol%, b = 25 mol%, c = 15 mol%, d = 50 mol%)
[Formula 18]
[Formula 19]
[Formula 20]
Experimental Example
A glass substrate (Eagle 2000; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and dried. Each of the photosensitive resin compositions prepared in Examples and Comparative Examples was spin coated on the glass substrate, and then prebaked at 90 ° C. for 80 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 200 μm, and light was emitted at an exposure amount (365 nm standard) of 60 mJ / cm 2 using an exposure machine (UX-1100SM; manufactured by Ushio Corporation). Investigate. In this case, a photomask in which the next pattern was formed on the same plane was used.
The coating film was immersed at 25 DEG C for 60 seconds in an aqueous developer having a circular opening (pattern) having a diameter of 14 mu m and a mutual interval of 100 mu m, and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation. It immersed and developed, and after washing with water, post-baking was performed at 235 degreeC for 15 minutes in oven. The obtained pattern height was 3.0 micrometers. The physical properties were evaluated for the pattern thus obtained as follows, and the results are shown in Table 2 below.
(1) phenomenon Residual rate evaluation
The prepared resist solution was applied to the substrate and spin coated, respectively, and then prebaked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature. Using the exposure machine (UX-1100SM; Ushio Corporation make), the light was irradiated to the whole surface of the coating film by the exposure amount (365 nm reference | standard) of 60 mJ / cm <2>.
After 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 ° C. for 60 seconds to develop. After washing with water, post-baking was performed at 230 ° C. for 30 minutes in an oven.
At this time, the film thickness after exposure and the film thickness after completion | finish of a postbaking process were measured, and the developing residual film rate was measured using the following formula.
The higher the residual film ratio, the better the performance.
(2) Developability evaluation
After spin-coating the prepared photosensitive resin composition on a glass substrate, prebaking is performed. Subsequently, the case where the coating film is dispersed in the form of fine particles by immersing the substrate in an aqueous developer containing 0.12% of the nonionic surfactant and 0.04% of potassium hydroxide is dissolved. In addition, the case where a coating film is lifted as it is is peeling.
Melting: O
Separation: △
Peel: X
(3) Residue evaluation
A glass substrate (Eagle 2000; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The photosensitive resin compositions prepared in Examples and Comparative Examples were spin coated on the glass substrates, and then prebaked at 90 ° C. for 80 seconds using a hot plate. After the prebaked substrate was cooled to room temperature, light was irradiated with an exposure dose (365 nm standard) of 60 mJ / cm 2 using an exposure machine (UX-1100SM; manufactured by Ushio) with an interval of 200 μm from a quartz glass photomask. . In this case, a photomask in which the next pattern was formed on the same plane was used.
The coating film was immersed at 25 DEG C for 60 seconds in an aqueous developer having a circular opening (pattern) having a diameter of 14 mu m and a mutual interval of 100 mu m, and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation. It was developed by dipping. The obtained pattern was observed using a Keyence microscope (VK-X200).
X is the case where no residue is observed.
No residue: X
Observation before the post bake, but after the post bake the residue has disappeared: △
Residue: ○
(4) Mechanical characteristic evaluation (total displacement and recovery rate)
Each of the photosensitive resin compositions prepared in Examples and Comparative Examples was spin coated on a glass substrate having a length of 2 inches (Eagle 2000; manufactured by Corning) and then prebaked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 200 μm and light was emitted at an exposure amount (365 nm standard) of 80 mJ / cm 2 using an exposure machine (UX-1100SM; manufactured by Ushio Co., Ltd.). Investigate. In this case, a photomask in which the next pattern was formed on the same plane was used.
The coating film was immersed at 25 ° C. for 60 seconds in an aqueous developer having a rectangular opening having a diameter of 12 μm, having a mutual interval of 100 μm, and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation. After washing with water, post-baking was performed at 235 ° C. for 15 minutes in an oven. The obtained pattern height was 3.0 micrometers. The pattern thus obtained was measured using a dynamic ultra-fine hardness tester (HM-2000; Helmut Fischer GmbH + Co.KG) to determine its total displacement (D1, μm) and elastic displacement (D2, μm) according to the following measurement conditions. Using the measured values, the recovery rate (%) was calculated as follows.
Recovery rate (%) = [elastic displacement (μm)] / [total displacement (μm)] × 100
Measurement conditions are as follows.
Test mode; Load-Unload Test
Test force; 50.0mN
Load speed; 4.41mN / sec
Holding time; 5sec
Indenter; Square pyramid indenter (50㎛ diameter)
Unformed
Unformed
(Μm)
(%)
Referring to Tables 1 to 3, in Examples 1 to 11 in which the polymeric compound containing succinic acid was increased in the composition, it is confirmed that the developability, the residual film ratio, and the mechanical properties are excellent overall.
Claims (8)
An alkali-soluble second resin including a repeating unit represented by Formula 2 below;
A polymerizable compound including a compound represented by Formula 3 below;
Photopolymerization initiator; And
A negative photosensitive resin composition comprising a solvent:
[Formula 1-1]
(Wherein R 4 , R 5 , R 6 and R 7 are each independently hydrogen or a methyl group,
R 8 is benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl) phenol propyl (meth) acrylate, 2-hydroxy- (3-phenyl) phenoxy propyl (meth) acrylate, N-benzylmaleimide, methyl (meth) acrylate, ethyl (meth) acrylic Latex, methoxy ethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tetraethylene glycol (meth) acrylate, phenoxyethylene glycol ( Meta) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) acrylate is a structure derived from a monomer selected from the group consisting of,
R 9 is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7),
R 10 is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- It is a structure derived from the monomer chosen from the group which consists of (meth) acryloyloxyethyl succinate,
R 11 is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol%, d = 5 to 50 mol%)
[Formula 2]
(Wherein, R 1 ′ is a hydrogen atom or a methyl group, R 2 ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 ′ is a hydrogen atom or a methyl group.
[Formula 3]
(In the formula,
R 31 is carbon or a saturated hydrocarbon group having 2 to 6 carbon atoms,
R 32 is independently of each other hydrogen, acryloyloxy group, succinate group or a straight or branched chain alkyl group having 1 to 5 carbon atoms,
n is an integer from 3 to 8,
The molecule represented by Formula 3 includes at least two acryloyloxy groups.
[Formula 2-1]
(Wherein R 16 and R 17 are each independently hydrogen or a methyl group,
R 18 is a structure derived from a monomer selected from the group consisting of the following formula (8),
Wherein R a is a single bond or alkylene having 1 to 6 carbon atoms, and the alkylene may further include an oxygen atom.
R 19 is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- A structure derived from a monomer selected from the group consisting of (meth) acryloyloxyethyl succinate,
e = 40 to 95 mol%, f = 5 to 60 mol%).
[Formula 4]
[Formula 5]
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