CN107219724B - Chemically amplified positive photosensitive organic insulating film resin composition and insulating film - Google Patents
Chemically amplified positive photosensitive organic insulating film resin composition and insulating film Download PDFInfo
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- CN107219724B CN107219724B CN201710063148.3A CN201710063148A CN107219724B CN 107219724 B CN107219724 B CN 107219724B CN 201710063148 A CN201710063148 A CN 201710063148A CN 107219724 B CN107219724 B CN 107219724B
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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Abstract
The present invention relates to a chemically amplified positive photosensitive organic insulating film resin composition and an insulating film. The chemically amplified positive photosensitive organic insulating film composition comprises (A) a binder resin, (B) a photoacid generator, (C) an additive and (D) a solvent, wherein the additive (C) is a compound represented by the following chemical formula 1, R in the following chemical formula 11Or R2Each independently is hydrogen or C1‑C6A linear or branched alkyl group, and m represents the number of repeating units in the main chain and is an integer of 1 to 15. The chemically amplified positive photosensitive organic insulating film composition of the present invention is excellent in chemical resistance to an etchant and a release agent, does not swell after development, can desirably maintain solubility in an alkaline aqueous solution as a developing solution, is excellent in sensitivity and transmittance, and exhibits an appropriate pattern angle, and therefore can be effectively used for producing an insulating film. Chemical formula 1
Description
Technical Field
The present invention relates to a chemically amplified positive photosensitive organic insulating film resin composition and an insulating film produced therefrom.
Background
Currently, TSP (touch screen panel) is being developed for large area, high transmittance, ultra-thin, light weight, and low price. In particular, in order to realize a large area and high resolution of the TSP display, it is essential to minimize a bezel (bezel) portion, and interest in development of electrode materials and engineering techniques for forming a fine electrode pattern of less than several tens of micrometers is increasing. In particular, the fine electrode patterns need to be electrically connected, and in this case, insulating films capable of electrically insulating each other are required.
In general, an organic insulating film is used as the insulating film, a photosensitive resin, which is a polymer compound that undergoes a chemical reaction with an electron beam to change its solubility in a specific solvent, is generally used as the organic insulating film, and a polar change or a crosslinking reaction of the polymer due to a photoreaction, such as a change in solubility of the organic insulating film in a developer such as an alkaline aqueous solution after exposure, is used for microfabrication of the electrode pattern.
The organic insulating film is divided into a positive type and a negative type according to the solubility of the photosensitive portion to the developer. Positive photoresist is a method in which an exposed portion is dissolved by a developer through a change in polarity to form a pattern; the negative photoresist is a pattern formed by dissolving an exposed portion in a developer through a crosslinking reaction and dissolving an unexposed portion.
Among them, the negative organic insulating film has a disadvantage of generating foreign matter when mixed with an alkaline developer widely used in the conventional production process, and unlike this, the positive organic insulating film has advantages as follows: the organic film is removed, so that the substrate can be significantly recovered and reused by removing the organic film when a defective panel is generated in the process.
However, in the conventional positive photosensitive organic insulating film composition, there is still a problem that the developer penetrates into the exposed portion and swells (swelling) even when developed with a photoresist, and the composition does not sufficiently satisfy the characteristics such as etching resistance represented by chemical resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 10-1404005
Disclosure of Invention
Problems to be solved
The present invention aims to provide a chemical amplification type positive photosensitive organic insulating film composition which can solve the problem that a developing solution still permeates into an exposed part and swells (swelling) when a conventional positive photosensitive organic insulating film composition is developed by a photoresist, an insulating film manufactured by using the chemical amplification type positive photosensitive organic insulating film composition, and an image display device comprising the insulating film.
Means for solving the problems
1. A chemically amplified positive photosensitive organic insulating film composition comprising (A) a binder resin, (B) a photoacid generator, (C) an additive and (D) a solvent,
the above (C) additive is a compound represented by the following chemical formula 1:
[ chemical formula 1]
(in the above-mentioned chemical formula 1,
r is as defined above1Or R2Each independently is hydrogen or C1-C6A linear or branched alkyl group, a cyclic or branched alkyl group,
m represents the number of repeating units in the main chain and is an integer of 1 to 15).
2. The chemically amplified positive photosensitive organic insulating film composition according to 1, wherein R is a compound of formula 11Or R2Each independently hydrogen.
3. The chemically amplified positive photosensitive organic insulating film composition according to 1, wherein the compound of formula 1 is contained in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the binder resin (a).
4. The chemically amplified positive photosensitive organic insulating film composition according to claim 1, wherein the binder resin (A) comprises (a-1) a resin in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected by an acid-decomposable group, (a-2) an oxetanyl group-containing acrylic resin, and (a-3) an epoxy group-containing acrylic resin.
5. The chemically amplified positive photosensitive organic insulating film composition according to the above 4, wherein the resin (a-1) contains a monomer represented by the following chemical formula 2 and is polymerized:
[ chemical formula 2]
(wherein R represents an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a tetrahydropyranyl group, or an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms).
6. The chemically amplified positive photosensitive organic insulating film composition according to the above 5, wherein the repeating unit formed of the monomer of the above chemical formula 2 is contained in an amount of 20 to 60 mol% based on the whole resin (a-1).
7. The chemically amplified positive photosensitive organic insulating film composition according to the above 4, wherein the resin (a-2) comprises a repeating unit represented by the following chemical formula 3:
[ chemical formula 3]
(in the formula, R1、R2And R3Each independently of the other being hydrogen or methyl,
R4is a structure derived from a monomer selected from the group consisting of the following formulae (1) to (3),
R5is a structure derived from a monomer selected from the group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate,
R6is a structure derived from a monomer represented by the following formula (4),
R7is an alkylene group having 1 to 6 carbon atoms,
R8is an alkyl group having 1 to 6 carbon atoms,
40 to 80 mol% for a, 5 to 45 mol% for b, and 10 to 55 mol% for c).
8. The chemically amplified positive photosensitive organic insulating film composition according to the above 4, wherein the resin (a-3) comprises a monomer represented by the following chemical formula 4 and is polymerized:
[ chemical formula 4]
(in the formula, R1Is a hydrogen atom or a methyl group; r2Is an alkylene group having 1 to 6 carbon atoms; r3And R4Each independently is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms, or may be linked to each other to form a ring of 3 to 8 carbon atoms; m is an integer of 1 to 6).
9. The chemically amplified positive photosensitive organic insulating film composition according to the above 8, wherein the repeating unit formed of the monomer represented by the above chemical formula 4 is contained in an amount of 5 to 60 mol% based on the whole (a-3) resin.
10. The chemically amplified positive photosensitive organic insulating film composition according to 4, wherein the binder resin comprises (a-1) 30 to 55 parts by weight of the resin, (a-2) 1 to 25 parts by weight of the resin, and (a-3) 30 to 60 parts by weight of the resin, based on 100 parts by weight of the total binder resin.
11. An insulating film obtained by curing the chemically amplified positive photosensitive organic insulating film composition described in any one of 1 to 10.
12. An image display device comprising the insulating film according to 11 above.
Effects of the invention
The chemically amplified positive photosensitive organic insulating film composition according to the present invention has excellent chemical resistance to an etchant and a release agent, does not swell after development, can desirably maintain solubility in an alkaline aqueous solution as a developer, has excellent sensitivity and transmittance, and exhibits an appropriate pattern angle, and thus can be effectively used for producing an insulating film.
Detailed Description
The invention provides a chemical amplification type positive photosensitive organic insulation film composition, which comprises (A) binder resin, (B) photoacid generator, (C) additive and (D) solvent, wherein the additive (D) is a compound represented by the following chemical formula 1:
[ chemical formula 1]
(in the above-mentioned chemical formula 1,
r is as defined above1Or R2Each independently is hydrogen or C1-C6A linear or branched alkyl group, a cyclic or branched alkyl group,
m represents the number of repeating units in the main chain and is an integer of 1 to 15).
According to the present invention, by including the additive represented by the above chemical formula 1 in the chemically amplified positive photosensitive organic insulating film composition, the composition is excellent in chemical resistance to an etchant and a stripper, does not swell after development, can desirably maintain solubility to an alkaline aqueous solution as a developing solution, is also excellent in sensitivity and transmittance, and exhibits an appropriate pattern angle, and thus can be effectively used in the production of an insulating film.
The chemically amplified positive photosensitive organic insulating film composition according to the present invention will be described in more detail below with reference to various aspects and embodiments of the present invention.
<Chemically amplified positive photosensitive organic insulating film composition>
The chemically amplified positive photosensitive organic insulating film composition of the present invention comprises (a) a binder resin, (B) a photoacid generator, (C) an additive represented by the following chemical formula 1, and (D) a solvent:
[ chemical formula 1]
(in the above-mentioned chemical formula 1,
r is as defined above1Or R2Each independently is hydrogen or C1-C6A linear or branched alkyl group, a cyclic or branched alkyl group,
m represents the number of repeating units in the main chain and is an integer of 1 to 15).
(A) Adhesive resin
The binder resin according to the present invention comprises three resins of (a-1) a resin in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected with an acid-decomposable group, (a-2) an oxetanyl group-containing acrylic resin, and (a-3) an epoxy group-containing acrylic resin.
The photosensitive resin composition of the present invention contains the three resins as a binder resin, and thus has excellent developability and can form a photosensitive pattern without leaving a residue.
[ resin (a-1) in which at least a part of the phenolic hydroxyl group or carboxyl group is protected with an acid-decomposable group ]
(a-1) the resin functions to impart solubility to the cured pattern by the photoacid generator during exposure.
The resin (a-1) is a resin containing a functional group in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected with an acid-decomposable group, and the functional group is not particularly limited, and a resin polymerized by containing a monomer represented by the following chemical formula 2 is exemplified.
[ chemical formula 2]
Wherein R is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a tetrahydropyranyl group, or an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms.
In the a-1 resin, the repeating unit formed by the monomer of the above chemical formula 2 may be properly mixed according to the specific kind of other monomer copolymerized and the like, and thus the content and the mixing ratio are not particularly limited, and for example, from 20 to 60 mol%, preferably from 30 to 60 mol%, is contained with respect to the whole of the a-1 resin from the aspect of pattern formation.
The a-1 resin (not protected by an acid-decomposable group) may further contain a repeating unit formed from a monomer having a phenolic hydroxyl group or a carboxyl group. Examples of such monomers include the above-mentioned ethylenically unsaturated monomers having a carboxyl group, hydroxystyrene, hydroxymethylstyrene, and the like.
From the viewpoint of improving the residual film rate and reducing the residue, the weight average molecular weight of the a-1 resin is preferably 5000 to 35000, more preferably 5000 to 20000.
[ acrylic resin (a-2) containing an oxetanyl group ]
The acrylic resin (a-2) containing an oxetanyl group according to the present invention exerts a function of improving developability and stability with time.
The oxetanyl group-containing acrylic resin (a-2) according to the present invention may preferably be a resin containing a repeating unit represented by the following chemical formula 3.
[ chemical formula 3]
In the formula, R1、R2And R3Each independently is hydrogen or methyl, R4Is a structure derived from a monomer selected from the group consisting of the following formulae (1) to (3),
R5is a structure derived from a monomer selected from the group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate,
R6is a structure derived from a monomer represented by the following formula (4),
R7is alkylene of 1 to 6 carbon atoms, R8Is an alkyl group having 1 to 6 carbon atoms,
40 to 80 mol% of a, 5 to 45 mol% of b, and 10 to 55 mol% of c.
The weight average molecular weight of the oxetanyl group-containing acrylic resin (a-2) is preferably 5000 to 30000, more preferably 8000 to 20000, from the viewpoints of reduction of residues due to improvement in developability and improvement in stability with time.
[ epoxy group-containing acrylic resin (a-3) ]
The acrylic resin (a-3) according to the present invention is a resin containing an epoxy group, and can be thermally cured, thereby enabling formation of a pattern with higher durability. The thermal curing may be performed, for example, in a post-baking process.
In order to introduce an epoxy group into an acrylic resin, in one embodiment of the present invention, the a-3 resin according to the present invention may be polymerized while including a monomer represented by the following chemical formula 4.
[ chemical formula 4]
In the formula, R1Is a hydrogen atom or a methyl group; r2Is an alkylene group having 1 to 6 carbon atoms; r3And R4Each independently is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms, or may be linked to each other to form a ring of 3 to 8 carbon atoms; m is an integer of 1 to 6.
The monomer represented by chemical formula 4 comprises a monomer represented by formula (II) and R2When the adjacent oxygen atom contains an oxygen atom in the chain, the glass transition temperature is lowered because the radius of rotation of the single bond is increased, and the fluidity is improved, and the processing is facilitated.
In chemical formula 4, the inclination of the formed pattern can be adjusted by adjusting the length of the single body by adjusting m, and in this case, the inclination of the pattern is decreased, so that the cured film can be prevented from being detached or cracked when the transparent electrode is deposited.
In the a-3 resin, the repeating unit containing an epoxy group, for example, the repeating unit of the monomer forming the above chemical formula 4 may be appropriately mixed according to the specific kind of other monomer copolymerized, etc., and the content and the mixing ratio are not particularly limited, and for example, it is preferable to contain 5 to 60 mol% with respect to the whole a-3 resin in view of maximizing the effect of improving transparency, improving the ease of processing, and preventing cracks from occurring in a cured film when a transparent electrode is deposited by adjusting the inclination of a pattern.
The (a-3) resin may be polymerized using a monomer known in the art capable of forming an acrylic resin, in addition to the monomer of chemical formula 4.
For example, an ethylenically unsaturated monomer having a carboxyl group can be used. The type of the ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids, dicarboxylic acids, acid anhydrides thereof, mono (meth) acrylates of monomers having a carboxyl group and a hydroxyl group at both terminals, and the like, and acrylic acid and methacrylic acid are preferable. These may be used alone or in combination of two or more.
In addition, at least one other monomer copolymerizable with the above-mentioned monomers may be contained for polymerization. For example, aromatic vinyl compounds; an N-substituted maleimide compound; alkyl (meth) acrylates; alicyclic (meth) acrylates; aryl (meth) acrylates; an unsaturated oxetane compound; (meth) acrylic acid esters ring-substituted with cycloalkane having 4 to 16 carbon atoms, bicycloalkane or tricycloalkane, etc., and preferably include aromatic vinyl compounds such as styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether and p-vinylbenzyl methyl ether; and alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [ 5.2.1.02, 6] decan-8-yl (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate. These may be used alone or in combination of two or more.
The weight average molecular weight of the epoxy group-containing acrylic resin (a-3) is preferably 5000 to 40000, preferably 15000 to 30000, from the viewpoint of improving developability and reducing residues.
The binder resin according to the present invention can significantly improve developability and reduce residue without degrading pattern formation performance by mixing the above three resins.
In the binder resin according to the present invention, the mixing ratio of the three resins is not particularly limited, and the mixing weight ratio of the a-1, a-3, a-2 resins is preferably 30 to 55 parts by weight of (a-1) resin, 1 to 25 parts by weight of (a-2) resin, and 30 to 60 parts by weight of (a-3) resin with respect to 100 parts by weight of the total binder resin, from the viewpoint of improving the residual film ratio and the stability with time.
The binder resin according to the present invention is not particularly limited in its content within a range capable of exerting its function, and for example, may be contained in an amount of 5 to 50% by weight, and may be preferably contained in an amount of 10 to 40% by weight, based on the total weight of the composition. When the content of the binder resin is within the above range, there is an advantage in that the effect of having an appropriate viscosity and improving sensitivity and decomposition performance can be maximized.
(B) Photoacid generators
The photoacid generator is a compound that generates an acid by irradiation of active light or radiation.
The kind of the photoacid generator is not particularly limited, and examples thereof include a diazonium salt-based photoacid generator,
Salt system, sulfonium salt system and iodine
Salt-based, sulfonimide-based, oxime sulfonate-based, diazodisulfone-based, disulfone-based, o-nitrobenzyl sulfonate-based, triazine-based compounds, and the like, and these may be used alone or in combination of two or more.
The content of the photoacid generator is not particularly limited within a range capable of exerting its function, and for example, may be contained in an amount of 0.1 to 20 parts by weight, and may preferably be contained in an amount of 0.5 to 10 parts by weight, with respect to 100 parts by weight of the binder resin. When the content of the photoacid generator is within the above range, chemical change due to the catalytic action of the acid can be sufficiently generated, and uniform coating can be achieved when the composition is coated.
In the present invention, a sensitizer may be further included together with the photoacid generator as necessary.
The sensitizer is a component that promotes the decomposition of the photoacid generator to improve sensitivity. The sensitizer according to the present invention is not particularly limited, and examples thereof include polynuclear aromatic compounds, xanthenes, xanthones, cyanines, oxones, thiazines, acridines, acridones, anthraquinones, squarylium, styryls, coumarins, anthracene compounds, and the like. These may be used alone or in combination of two or more.
Preferably, the sensitizer according to the present invention may be a compound of the following chemical formula 5.
[ chemical formula 5]
In the formula, R1And R2Each independently an alkyl group having 1 to 6 carbon atoms.
The sensitizer of chemical formula 5 may preferably be a compound of chemical formulae 6 to 8 below.
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
The content of the sensitizer is not particularly limited within the range in which the sensitizer can function, and for example, may be contained in an amount of 0.01 to 60 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the binder resin. When the content of the sensitizer is within the above range, there is an advantage that the sensitivity or transmittance can be improved to the maximum by spectral sensitization.
(C) Additive agent
The photosensitive resin composition of the present invention includes an additive represented by the following chemical formula 1:
[ chemical formula 1]
(in the above-mentioned chemical formula 1,
r is as defined above1Or R2Each independently is hydrogen or C1-C6A linear or branched alkyl group, a cyclic or branched alkyl group,
m represents the number of repeating units in the main chain and is an integer of 1 to 15).
The additive compound of chemical formula 1 according to the present invention includes a large amount of aromatic ring structures and side chain structures, and thus has high hydrophobicity, and can prevent swelling development. Further, the-OH group can improve adhesion to a metal, and the cyclohexane functional group having the carboxyl group not only can increase developability, but also can increase reliability of a cured film because of high reactivity with oxetane.
In addition, as a preferred example according to the present invention, R of the compound of the above chemical formula 11Or R2May each independently be hydrogen.
In addition, according to the present invention, when the integer m of the compound of chemical formula 1 is greater than 15, developability or sensitivity is reduced. In this respect, m of the above chemical formula 1 of the present invention may be preferably an integer of 3 to 12, more preferably an integer of 4 to 8.
In the present invention, the compound of the above chemical formula 1 may be contained in an amount of 0.1 to 3 parts by weight with respect to 100 parts by weight of (a) the binder resin.
As a preferable example, when the compound of chemical formula 1 is contained in an amount of less than 0.1 part by weight based on 100 parts by weight of the binder resin, there is a problem that swelling development is severe and fine patterns are difficult to form, and there is a possibility that defects may occur in a subsequent process, and when the compound of chemical formula 1 is contained in an amount of more than 3 parts by weight based on 100 parts by weight of the binder resin, there is a possibility that sensitivity is significantly lowered and residues are generated.
On the other hand, in addition to the additive represented by the above chemical formula 1 of the present invention, additives such as a basic compound, a surfactant, an adhesion improver, a thermal crosslinking agent, a light stabilizer, a light curing accelerator, an anti-halation agent (leveling agent), and a defoaming agent, which are generally used, may be further included within a range not departing from the object of the present invention.
(D) Solvent(s)
The type of the solvent is not particularly limited, and any solvent can be used as long as it can dissolve the above components, has an appropriate drying rate, and can form a uniform and smooth coating film after evaporation of the solvent.
Specific examples thereof include ethers, acetates, esters, ketones, amides, lactones, and the like. These may be used alone or in combination of two or more.
Preferably, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ethyl ether, or a mixture thereof is used from the viewpoint of coatability and uniformity of the film thickness of the insulating film coating.
The solvent is not particularly limited in its content within a range capable of performing its function, and for example, may be included in an amount of 40 to 90% by weight, and may preferably be included in an amount of 50 to 80% by weight, based on the total weight of the composition. If the content of the solvent is 40 to 90 wt% based on the total weight of the composition, there is an advantage that the solid content and viscosity can be maintained at appropriate levels to increase the coatability.
<Insulating film>
The present invention provides an insulating film produced using the above composition.
The insulating film forming method according to the present invention may include: a step of applying the photosensitive resin composition of the present invention to the upper part of a substrate of a display device or to the upper part of a source/drain or a silicon nitride layer formed on the substrate; a step of subjecting the photosensitive resin composition to pre-baking (pre-make); selectively exposing and developing the photosensitive resin composition to form a pattern; and a step of heat-treating the formed pattern.
As the substrate, glass or a transparent plastic resin which is generally used for a liquid crystal display device, an organic E L, or the like is mainly used, but is not particularly limited and used according to the characteristics of a display device to be used.
<Image display device>
The present invention also provides an image display device including the insulating film.
The insulating film of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.
The image display device may further include a structure generally used in the art in addition to the insulating film.
The present invention will be described in further detail with reference to examples and the like, but the scope and content of the present invention are not to be construed as being narrowed or limited by the examples and the like below. In addition, it should be clear that if the present invention is based on the disclosure of the present invention including the following examples, those skilled in the art can easily carry out the present invention without disclosing specific experimental results, such variations and modifications are certainly included in the scope of the present invention claimed.
Examples 1 to 15 and comparative examples 1 to 2
Photosensitive resin compositions having the compositions and contents shown in table 1 below were produced.
[ Table 1]
1. Binder resin (A)
A1-1、A1-2：
A1-1：(a)/(b)＝60/40，Mw＝12000
A1-2：(a)/(b)＝70/30，Mw＝12000
A2-1、A2-2：
A2-1：(a)/(b)/(c)＝60/20/20，Mw＝8000
A2-2：(a)/(b)/(c)＝60/10/30，Mw＝8000
A3-1、A3-2：
A3-1：(a)/(b)/(c)/(d)＝15/10/50/25，Mw＝25000
A3-2：(a)/(b)/(c)/(d)＝25/15/30/30，Mw＝25000
2. Photoacid generators (B)
3. Photosensitizer (C)
4. Solvent (D)
D1: propylene glycol methyl ethyl acetate
D2: diethylene glycol methyl ethyl ether
5. Basic compound (E): dicyclohexylmethylamine
6. Additive (F)
F1：
F2：
F3：
7. Coupling agent (G): KBM-403 (Gamma-glycidoxypropyltrialkoxysilane)
8. Surfactant (H):
H1：SH-8400，H2：F-475
examples of the experiments
The resin compositions produced in examples and comparative examples were evaluated as follows, and the results are shown in table 2 below.
(1) Sensitivity measurement
The photosensitive resin compositions of examples and comparative examples were applied to a glass substrate (Corning 1737, manufactured by Corning Inc.) having a thickness of 0.7mm by a spin coater, and heated on a hot plate at 100 ℃ for 125 seconds to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 4.0. mu.m.
Then, in order to obtain a contact hole pattern having a diameter of 10 μm, the exposure portion was exposed by an i-line stepper (NSR-205i11D, Nikon corporation) for a mask having a square pattern opening with a side of 10 μm.
The exposed substrate was subjected to Puddle Development (Puddle Development) at 23 ℃ for 40 seconds using a 2.38% aqueous tetramethylammonium hydroxide solution as a developer, and heated in an oven at 230 ℃ for 30 minutes to obtain a cured film.
The substrate was then vertically cut, and the exposure amount to become a 10 μm contact hole was selected as the sensitivity in each composition.
(2) Pattern angle
The pattern obtained in experimental example (1) was cut perpendicularly, and the angle to the substrate was calculated from an optical (SEM) photograph.
(3) Transmittance measurement
The transmittance at 400nm of the film obtained in experimental example (1) was measured with a spectrophotometer.
(4) Evaluation of degree of swelling (swelling) of etching solution
The photosensitive resin compositions of examples and comparative examples were applied to a glass substrate (Corning 1737, Corning Co.) having a thickness of 0.7mm by a spin coater, and heated on a heating plate at 100 ℃ for 125 seconds to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 4.0. mu.m. The formed film was immersed in an etching solution at 45 ℃ for 120 seconds, and the film thickness before and after immersion was measured to evaluate the degree of swelling.
Swelling (%) - (film thickness after immersion-film thickness before immersion) × 100
◎：100％～102％
○：103％～106％
△：106％～107％
X: over 108 percent
(5) Evaluation of degree of swelling (swelling) of Release agent
The photosensitive resin compositions of examples and comparative examples were applied to a glass substrate (Corning 1737, Corning Co.) having a thickness of 0.7mm by a spin coater, and heated on a hot plate at 100 ℃ for 125 seconds to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 4.0. mu.m. The resulting film was immersed in a water-based release agent at 60 ℃ for 120 seconds, and the film thickness before and after immersion was measured to evaluate the degree of swelling.
Swelling (%) - (film thickness after immersion-film thickness before immersion) × 100
◎：100％～102％
○：103％～106％
△：106％～107％
X: over 108 percent
[ Table 2]
Referring to table 2 above, it was confirmed that the insulating films formed from the photosensitive resin compositions of examples 1 to 12 were excellent in chemical resistance to an etching solution and a stripper, and in addition, were also excellent in sensitivity and transmittance, showing an appropriate pattern angle.
However, it was confirmed that the chemical resistance-improving effect was somewhat lowered in example 13 in which a small amount of the additive was used; it was confirmed that in example 14 in which an excessive amount of the additive was used, although the chemical resistance was improved, the exposure amount was increased slightly and the sensitivity was somewhat lowered; the composition of example 15 showed a result that although swelling became good, sensitivity was somewhat lowered.
On the other hand, the compositions of comparative examples 1 to 2 exhibited severe swelling.
Therefore, according to the present invention, if the additive of the present invention is used, it is excellent in chemical resistance to an etching solution and a stripping agent, does not swell after development, can desirably maintain solubility in an alkaline aqueous solution as a developing solution, is also excellent in sensitivity and transmittance, and exhibits an appropriate pattern angle, and thus can be effectively used in the production of an insulating film.
Claims (12)
1. A chemically amplified positive photosensitive organic insulating film composition comprising (A) a binder resin, (B) a photoacid generator, (C) an additive and (D) a solvent,
the (C) additive is a compound represented by the following chemical formula 1:
chemical formula 1
In the chemical formula 1 described above,
the R is1Or R2Each independently is hydrogen or C1-C6A linear or branched alkyl group, a cyclic or branched alkyl group,
m represents the number of repeating units in the main chain and is an integer of 1 to 15.
2. The chemically amplified positive photosensitive organic insulator of claim 1Film composition, R of the compound of chemical formula 11Or R2Each independently hydrogen.
3. The chemical amplification type positive photosensitive organic insulating film composition according to claim 1, wherein the compound of chemical formula 1 is contained in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the (a) binder resin.
4. The chemically amplified positive photosensitive organic insulating film composition according to claim 1, wherein the binder resin (A) comprises (a-1) a resin in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected by an acid-decomposable group, (a-2) an oxetanyl group-containing acrylic resin, and (a-3) an epoxy group-containing acrylic resin.
5. The chemical amplification type positive photosensitive organic insulating film composition according to claim 4, wherein the resin (a-1) comprises a monomer represented by the following chemical formula 2 and is polymerized:
chemical formula 2
Wherein R is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a tetrahydropyranyl group, or an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms.
6. The chemically amplified positive photosensitive organic insulating film composition according to claim 5, wherein the repeating unit formed from the monomer of chemical formula 2 is contained in an amount of 20 to 60 mol% based on the whole resin (a-1).
7. The chemical amplification type positive photosensitive organic insulating film composition according to claim 4, wherein the resin (a-2) comprises a repeating unit represented by the following chemical formula 3:
chemical formula 3
In the formula, R1、R2And R3Each independently of the other being hydrogen or methyl,
R4is a structure derived from a monomer selected from the group consisting of the following formulae (1) to (3),
R5is a structure derived from a monomer selected from the group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate,
R6is a structure derived from a monomer represented by the following formula (4),
R7is an alkylene group having 1 to 6 carbon atoms,
R8is an alkyl group having 1 to 6 carbon atoms,
40 to 80 mol% of a, 5 to 45 mol% of b, and 10 to 55 mol% of c.
8. The chemical amplification type positive photosensitive organic insulating film composition according to claim 4, wherein the resin (a-3) comprises a monomer represented by the following chemical formula 4 and is polymerized:
chemical formula 4
In the formula, R1Is a hydrogen atom or a methyl group; r2Is an alkylene group having 1 to 6 carbon atoms; r3And R4Each independentlyA hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to form a ring having 3 to 8 carbon atoms; m is an integer of 1 to 6.
9. The chemical amplification type positive photosensitive organic insulating film composition according to claim 8, wherein the repeating unit formed from the monomer represented by chemical formula 4 is contained in an amount of 5 to 60 mol% based on the whole (a-3) resin.
10. The chemical amplification type positive photosensitive organic insulating film composition according to claim 4, wherein the binder resin comprises (a-1) 30 to 55 parts by weight of the resin, (a-2) 1 to 25 parts by weight of the resin, and (a-3) 30 to 60 parts by weight of the resin, relative to 100 parts by weight of the total binder resin.
11. An insulating film obtained by curing the chemically amplified positive photosensitive organic insulating film composition according to any one of claims 1 to 10.
12. An image display device comprising the insulating film according to claim 11.
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| KR10-2016-0033135 | 2016-03-21 | ||
| KR1020160033135A KR20170109264A (en) | 2016-03-21 | 2016-03-21 | Chemically amplified positive photosensitive resin composition for an organic insulation film and insulation layer prepared from the same |
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| CN107219724B true CN107219724B (en) | 2020-07-14 |
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| TWI518458B (en) * | 2008-03-28 | 2016-01-21 | 富士軟片股份有限公司 | Positive type photosensitive resin composition and curing film forming method using it |
| KR101357604B1 (en) * | 2010-11-12 | 2014-02-03 | 연세대학교 산학협력단 | Conductive transparent adhesive composition and adhesive prepared by using the same |
| JP5531034B2 (en) * | 2012-01-31 | 2014-06-25 | 富士フイルム株式会社 | Photosensitive resin composition, method for forming cured film, cured film, organic EL display device and liquid crystal display device |
| JP6327066B2 (en) * | 2013-09-03 | 2018-05-23 | 住友化学株式会社 | Compound, resin, resist composition, and method for producing resist pattern |
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