KR20150146434A - Photo-crosslinking resin composition, insulating film and oled formed by using the same - Google Patents
Photo-crosslinking resin composition, insulating film and oled formed by using the same Download PDFInfo
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- KR20150146434A KR20150146434A KR1020150086881A KR20150086881A KR20150146434A KR 20150146434 A KR20150146434 A KR 20150146434A KR 1020150086881 A KR1020150086881 A KR 1020150086881A KR 20150086881 A KR20150086881 A KR 20150086881A KR 20150146434 A KR20150146434 A KR 20150146434A
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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Abstract
Description
The present invention relates to a photo-crosslinkable resin composition, and more particularly to a photo-crosslinkable resin composition comprising a polyamic acid resin as an alkali-soluble resin, an unsaturated ethylenic monomer, a photopolymerization initiator, and a liquid repellent polymer containing a fluoroalkyl acrylate, And an organic light emitting device.
In general, a resist material for forming an ITO electrode such as a liquid crystal display (LCD) or an organic EL display, an interlayer insulating film, a circuit protective film, a colored pigment dispersion resist for the production of a color filter of a liquid crystal display, A photocurable resin composition is widely used as a film forming material. Among them, in recent years, demand for liquid crystal displays and OLEDs for televisions has been increasing, and photo-crosslinkable resin compositions are widely used in the production process. BACKGROUND ART [0002] In the manufacture of color filters, there is a strong demand for cost reduction due to the increase in demand, and an ink jet method capable of being manufactured at low cost has been proposed.
In the production of a color filter by the ink-jet method, a method of forming a pixel by forming a partition defining a pixel in advance by photolithography or the like, and then applying ink, which is red, green and blue, Is characterized in that the process is simpler and the waste of ink is less than that of the conventional method using a pigment-dispersed resist. However, in this ink-jet method, when ink droplets are dropped onto the pixel portion, the substrates and the side surfaces of the barrier ribs require adhesion with ink, and ink affinity is required. However, a situation in which ink droplets flow over the adjacent pixels beyond the partition walls is prevented It is required to have lyophobicity on the surface of the partition wall in order to prevent color mixing of ink between neighboring pixel regions.
SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art,
Capable of realizing a high sensitivity circuit without residue and capable of enhancing light transmittance and securing a low dielectric constant at the same time.
Further, the present invention provides an insulating film which has a contact angle with respect to propylene glycol monomethyl ether acetate (PGMEA) of 40 degrees or more by containing the above-mentioned photo-crosslinkable resin composition and prevents blurring of a luminescent material soluble between pixel spaces .
It is another object of the present invention to provide an organic light emitting diode (OLED) capable of improving a contrast ratio by using the above-mentioned photo-crosslinkable resin composition and realizing a high sensitivity pattern.
(A), an unsaturated ethylenic monomer (B), a photopolymerization initiator (C) and a liquid repellent polymer (D), wherein the alkali-soluble resin (A) Is a polyamic acid containing a repeating unit represented by the following formula (2), and the liquid repellent polymer (D) comprises a fluoroalkyl acrylate represented by the following formula (1).
[Chemical Formula 1]
In Formula 1, A is a fluoroalkyl group (Rf) or a perfluorinated polyether group (PFPE) of C1 to C10, B is H, CH 3 or halogen,
(2)
Wherein R 1 and R 2 are the same or different and each independently is a divalent to octavalent organic group having at least two carbon atoms, R 3 and R 4 are the same or different, X is an integer of 0 to 2, y is an integer of 0 to 4, x + y > 0, and z is an integer of 0 to 2, or an organic group of 1 to 12 carbon atoms, And n is an integer of 10 to 200. [
The present invention also provides an insulating film formed by curing the photo-crosslinkable resin composition.
Also, the present invention provides an organic light emitting device including the insulating film.
The photo-crosslinkable resin composition of the present invention is capable of realizing a highly sensitive circuit without residues, has excellent light transmittance, and has little outgassing at high temperature after solvent removal.
In addition, an insulating film having a low dielectric constant and a contact angle of 40 degrees or more with respect to propylene glycol monomethyl ether acetate (PGMEA) can be prepared by curing the photo-crosslinkable resin composition of the present invention.
Also, an organic insulating material of an organic light emitting diode (OLED) capable of realizing intaglio resolution can be manufactured using the photocurable resin composition of the present invention, and an organic luminescent device capable of realizing a high sensitivity pattern by improving a contrast ratio can be manufactured .
Fig. 1 is an optical image patterned using the photo-crosslinkable resin composition according to Example 1 of the present invention. Fig.
Unless otherwise defined, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
Throughout this specification, when an element is referred to as "including" an element, it is understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.
Hereinafter, the present invention will be described in more detail.
The alkali-soluble resin (A) comprises an alkali-soluble resin (A), an unsaturated ethylenic monomer (B), a photopolymerization initiator (C) and a liquid repellent polymer (D) Wherein the liquid repellent polymer (D) comprises a fluoroalkyl acrylate represented by the following formula (1): < EMI ID = 1.0 >
[Chemical Formula 1]
In Formula 1, A is a fluoroalkyl group (Rf) or a perfluorinated polyether group (PFPE), B is H, CH 3 or halogen,
(2)
Wherein R 1 and R 2 are the same or different and each independently is a divalent to octavalent organic group having at least two carbon atoms, R 3 and R 4 are the same or different, X is an integer of 0 to 2, y is an integer of 0 to 4, x + y > 0, and z is an integer of 0 to 2, or an organic group of 1 to 12 carbon atoms, And n is an integer of 10 to 200. [
Wherein the photo-crosslinkable resin composition comprises 5 to 80 parts by weight of an unsaturated ethylenic monomer (B), 0.5 to 10 parts by weight of a photopolymerization initiator (C) and 0.5 to 10 parts by weight of a fluoroalkyl acrylate, based on 100 parts by weight of the alkali- And 0.5 to 10 parts by weight of the liquid preparation polymer (D).
Hereinafter, the constituent components of the photo-crosslinkable resin composition of the present invention will be described.
The alkali-soluble resin (A)
The alkali-soluble resin of the present invention serves as a binder and is a polyamic acid containing a repeating unit represented by the following formula (2).
(2)
Wherein R 1 and R 2 are the same or different and each independently is a divalent to octavalent organic group having at least two carbon atoms, R 3 and R 4 are the same or different, X is an integer of 0 to 2, y is an integer of 0 to 4, x + y > 0, z is an integer of 0 to 2, , and n is an integer of 10 to 200.
In Formula 2, R 1 and R 2 are the same or different from each other, and each independently represents a group containing at least one phenyl group and a hydrocarbon group of C 0 to C 10, and the carbon of the hydrocarbon group is an ether group (-O- ) And a sulfonic group (-SO 2 -), and the hydrocarbon group may have a fluorine group (F) as a substituent, x and y are each an integer of 0 to 2, and x + y> 0 And z is an integer of 1 to 2.
In the above formula (2), R 1 and R 2 are the same or different and each independently a diphenyl group containing a fluoroalkyl group having 2 to 8 carbon atoms in terms of polymerization and imidization. For example, it may be - [(C 6 H 3 ) 2 C (CF 3 ) 2 ] -. In the formula (2), R 3 and R 4 are the same or different and each independently is an organic group having 1 to 4 carbon atoms including a hydroxy group, or hydrogen, from the viewpoint of development. More preferably an organic group having 1 to 2 carbon atoms including a hydroxy group.
In the general formula (2), n is preferably an integer of 10 to 200 in terms of solubility, more preferably an integer of 20 to 50.
As the alkali-soluble resin of the present invention, for example, a polyamic acid resin can be produced as an alkali-soluble resin by polymerizing an aromatic diamine and an aromatic dianhydride in a first solvent. this is The polyamic acid resin may be prepared by adding an additive to a polyamic acid resin which is an imide precursor without imidization proceeding or by precipitating the polyamic acid resin obtained in a second solvent followed by filtration and drying.
The aromatic diamine is not particularly limited and may be selected from the group consisting of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis- Aminophenoxy) -phenyl] propane (6HMDA), 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl (2,2'-TFDB), 3,3'-bis (3,3'-TFDB), 4,4'-bis (3-aminophenoxy) diphenyl sulfone (DBSDA), bis (3- Aminophenyl) sulfone (3DDS), bis (4-aminophenyl) sulfone (4DDS), 1,3-bis (3-aminophenoxy) benzene ) Benzene (APB-134), 2,2'-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), 2,2'- Phenyl] hexafluoropropane (4-BDAF) and oxydianiline (ODA) can be used. In particular, use of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis-AP-AF) is more preferable in that it has excellent light transmittance and heat resistance.
Examples of the aromatic dianhydride include, but are not limited to, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2,5-dioxotetrahydrofuran- 3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), 4,4 '- (4,4'-isopropylidene diphenoxy) Bis (phthalic anhydride) (HBDA), 3,3 '- (4,4'-oxydiphthalic dianhydride) (ODPA) and 3,4,3', 4'- biphenyltetracarboxylic Dianhydride (BPDA), and the like may be used. In particular, it is more preferable to use 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydride (6FDA) because it has excellent light transmittance and heat resistance.
The above-mentioned aromatic diamine and aromatic dianhydride are dissolved in a first solvent at a molar ratio of 1: 0.80 to 1: 1, and then polymerized to prepare a polyamic acid resin. If the molar ratio of the aromatic dianhydride to the aromatic dianhydride is less than 0.80 mol per mol of the aromatic diamine, the molecular weight of the resulting polyamic acid after polymerization of the aromatic diamine and the aromatic dianhydride may be so low that the yield and pattern processability may be significantly deteriorated, If it exceeds 1 mole, it is difficult to stabilize the molecular weight of the polyamic acid, and it may become difficult to obtain a constant molecular weight.
The polyamic acid resin thus prepared has a viscosity of 50 to 200 cps, and thus a polyamic acid having a weight average molecular weight of 10,000 to 40,000 g / mol capable of realizing a high sensitivity pattern can be produced. Generally, since the viscosity has a proportional increase / decrease relationship with the final weight average molecular weight, if the viscosity of the polyamic acid resin is out of the above range, the weight average molecular weight becomes too large or small, .
The conditions for the polymerization reaction are not particularly limited, but the reaction temperature is preferably 15 to 25 占 폚 in terms of polymerization rate, and the reaction time is preferably 20 minutes to 5 hours. Oxygen may act as a polymerization inhibitor during the reaction and is preferably carried out in an inert atmosphere such as argon or nitrogen.
On the other hand, in the production of the polyamic acid resin, in view of the polymerization efficiency, the aromatic diamine and the aromatic dihydride may be polymerized in the first solvent, and the photopolymerization initiator and the unsaturated ethylenic monomer may be immediately added to the polymerized resin. In addition, when the polymerized polyamic acid resin is precipitated and dried to use a powdered polyamic acid, a photopolymerization initiator and an unsaturated ethylenic monomer may be used by using a solvent (E).
The first solvent for the polymerization of the above monomers is not particularly limited as long as it is a solvent capable of dissolving the polyamic acid. Specific examples of the first solvent include m-cresol, propylene glycol monomethyl ether acetate (PGMEA), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc) Dimethyl sulfoxide (DMSO), acetone, and diethyl acetate. In addition, tetrahydrofuran (THF), chloroform, and gamma -butyrolactone may be used. However, no.
The content of the first solvent is not particularly limited, but is preferably 50 to 95% by weight, more preferably 70 to 90% by weight in the total polyamic acid solution in order to obtain an appropriate polyamic acid solution viscosity.
In the present invention, the polymerized polyamic acid resin is precipitated and dried to recover the powdered polyamic acid, which is then dissolved in the solvent (E) to prepare a photocurable resin composition.
At this time, the principle of precipitating the polyamic acid resin into the solid matter by the difference in solubility can be applied by using a second solvent which can not dissolve the polyamic acid polymer, in order to precipitate the polyamic acid resin. The second solvent may have a lower polarity than the first solvent. Specifically, at least one selected from the group consisting of non-polar solvents such as water, alcohols and hexene, ethers and ketones may be selected and used.
In this case, the content of the second solvent is not particularly limited, but is preferably 200 to 1000 parts by weight based on 100 parts by weight of the polyamic acid solution. When it is used in an amount less than 200 parts by weight, precipitation and purification may be difficult, and when it is used in an amount exceeding 1000 parts by weight, the work is not easy.
As described above, the polyamic acid resin contained in the second solvent is prepared by filtration and drying. In this case, the filtration and drying conditions are preferably carried out at a temperature of 50 to 100 ° C. for 12 to 24 hours in consideration of the boiling points of the first solvent remaining in the second solvent and the solidified polyamic acid resin.
The polyamic acid resin produced by the above-mentioned method preferably has a weight average molecular weight (based on GPC measurement) of 10,000 to 40,000 g / mol. When the weight average molecular weight of the polyamic acid resin is within the above range, it is possible to achieve a good resolution in the pattern process.
The 'weight average molecular weight' in the above and below is defined as the conversion of polystyrene equivalent, as determined by gel permeation chromatography (GPC).
Unsaturation Ethylene-based Monomer (B)
In the present invention, the unsaturated ethylenic monomer is a monofunctional or multifunctional acrylic monomer having at least one unsaturated ethylene bond, which serves as a crosslinked backbone in the photo-crosslinkable resin composition. More preferably, it is monofunctional, bifunctional or trifunctional or more (meth) acrylate, which is preferable from the viewpoints of good polymerizability and improved heat resistance and surface hardness of the resulting protective film.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl And 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, but are not limited thereto.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexadiol (meth) acrylate, 1,9-nonanediol (meth) (Meth) acrylate, tetraethylene glycol (meth) acrylate and bisphenoxy ethyl alcohol fluorene diacrylate, but are not limited thereto.
Examples of the trifunctional or higher functional (meth) acrylate include trihydroxy ethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.
These monofunctional, bifunctional and trifunctional (meth) acrylates may be used alone or in combination.
The unsaturated ethylenic monomer is contained in an amount of 5 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the unsaturated ethylenic monomer is within the above range, it is good in terms of pattern, adhesive strength and hardness, and has an advantage of facilitating the developing process.
Light curing Initiator (C)
The photo-crosslinkable resin composition of the present invention comprises a photopolymerization initiator. In the present invention, the photopolymerization initiator means a compound which generates an active species capable of initiating polymerization of the unsaturated ethylenic monomer such as a radical, anion or cation, causing decomposition or bonding by exposure. The photopolymerization initiator serves to cause the above-mentioned unsaturated ethylenic monomer (B) to undergo a chemical curing reaction.
The photopolymerization initiator (C) may be any photopolymerization initiator known in the art without limitation. Specific examples thereof include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4 , 4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, a, a'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy- 2-methylamino-1- (4-morpholinophenyl) -methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] 2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2- Ketones such as 1-hydroxycyclohexyl phenyl ketone; Quinones such as anthraquinone 1,4-naphthoquinone; Tri (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2- chlorophenyl) (Trichloromethyl) -s-triazine, 2,2,2-trifluoroethyl methacrylate (2,2,2-trimethylphenyl) -s-triazine, phenacyl chloride, tribromomethylphenylsulfone, Halogenated compounds such as trifluoroethyl methacrylate); Peroxides such as di-t-butyl peroxide, and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; But is not limited thereto.
In the photoconductive resin composition of the present invention, the photopolymerization initiator may be contained in an amount of 0.5 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the amount of the photopolymerization initiator is less than 0.5 parts by weight or exceeds 10 parts by weight, problems of low sensitivity and low permeability may occur.
A liquid preparation Polymer (D)
The photo-crosslinkable resin composition of the present invention comprises a liquid repellent polymer (D). The liquid repellent polymer is characterized by containing a fluoroalkyl acrylate represented by the following formula (1).
[Chemical Formula 1]
In the above formula (1), A is a fluoroalkyl group (Rf) or a perfluoropolyether group (PFPE), and B is H, CH 3 or halogen.
In the present invention, the liquid repellent polymer is included in the liquid-repellent region when the functional material ink is applied onto the substrate, so that the ink is spontaneously diffused and wetted only in the liquid-repellent region by avoiding the liquid-repellent region. As a result, it is possible to perform the role of an additive compound which enables fine patterning and liquid-repellency, which is not limited to the processing accuracy of the coating apparatus, when applying the ink.
In the present invention, the liquid repellent polymer includes a fluoroalkyl acrylate. The content of the repellent polymer is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin. If the amount is less than 0.5 parts by weight, a desired contact angle with respect to propylene glycol monomethyl ether acetate (PGMEA) If it exceeds the weight part, there may be a residue problem of the developed part after the development.
Examples of the liquid repellent polymer include, but are not limited to, fluoroalkyl acrylate / methacrylic acid (MAA) / hydrocarbon methacrylate (Rh-MA) (manufactured by DAKIN). The above-mentioned compound is a compound obtained by applying fluoroalkyl acrylate for dynamic lyophobicity of a resist film and applying methacrylic acid for solubility and crosslinkability in an alkaline developer.
Solvent (E)
The photo-crosslinkable resin composition of the present invention may further comprise a solvent (E) capable of maintaining a solid content and viscosity. Examples of the solvent (E) include, but are not limited to, alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether and ethylene glycol monoethyl ether; Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanal; Acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Examples of the solvent include methyl esters, ethyl esters, propyl esters, butyl esters, ethyl esters of 2-hydroxypropionic acid, ethyl esters of 2-hydroxy-2-methylpropionic acid, methyl esters of ethyl esters of hydroxyacetic acid, Ester, butyl ester, methyl ester of butoxyacetic acid, ethyl ester, butyl ester, methyl ester of propoxyacetic acid, butyl ester, methyl ester of butoxyacetic acid, ethyl lactate, butyl lactate, Ethyl esters, propyl esters, butyl esters, methyl esters, ethyl esters, propyl esters, butyl esters of 2-methoxypropionic acid, methyl esters, ethyl esters, propyl esters, butyl esters, 3-methoxypropane Methyl ester, ethyl ester, propyl < RTI ID = 0.0 > Esters such as methyl esters, ethyl esters, propyl esters, butyl esters and methyl esters of 3-butoxypropionic acid, ethyl esters, propyl esters and butyl esters of butyl, butyl and 3-ethoxypropionic acid, It is not limited. One or more kinds selected from the group consisting of these can be used singly or in combination.
It is more preferable to use diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate or the like in view of the solubility in the solvent, the reactivity with each component, and the convenience of forming a coating film.
The solvent may be contained in an amount of 10 to 90 parts by weight based on 100 parts by weight of the alkali-soluble resin. If it is out of the above range, there may be a problem in smooth coating. When the content of the solvent is within the above range, the coating property is good when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (die coater) and an ink jet.
The photo-crosslinkable resin composition of the present invention can be generally used in a photo-crosslinkable resin composition for the purpose of improving specific functions such as a surfactant, a silicone leveling agent, a filler and an antioxidant depending on the needs of the person skilled in the art, Lt; RTI ID = 0.0 > additive < / RTI > These additives can be arbitrarily selected from materials widely used in the field to which the present invention belongs.
The present invention also includes an insulating film containing the above-mentioned photo-crosslinkable resin composition. A method of manufacturing an insulating film of an organic light emitting device using the photo-crosslinkable resin composition according to the present invention is described below.
The light-bridging resin composition of the present invention may be applied to the surface of the substrate by coarsening, and the film may be formed by a preliminary heat treatment. A spin coater or the like can be used as a coating method, and the prebaking conditions are usually 100 to 120 ° C for 1 to 3 minutes, using a hot plate, depending on the composition ratio. At this time, the thickness of the dielectric layer is adjusted to be in the range of 3.0 to 4.0 mu m. Next, the preliminarily heat-treated coating film is irradiated with ultraviolet rays using a mask and developed with an alkaline developer to remove unnecessary portions to form a pattern. The amount of exposure is determined according to the resolution, and the developing solution uses an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia as an aqueous alkaline solution. In particular, the development is carried out in a 2.38% aqueous solution of TMAH (Tetra Methyl Ammonium Hydroxide) .
Thereafter, development can be performed using a spraying method, a dipping method, or the like. The insulating film can then be completed through a postbake using a hot plate. At this time, it is preferable to heat postbake at 200 to 250 ° C for 30 to 60 minutes.
The insulating film produced by the photo-crosslinkable resin composition of the present invention has hydrophobicity having a contact angle with respect to propylene glycol monomethyl ether acetate (PGMEA) of not less than 40 degrees (°) while having excellent pattern developability, light transmittance and insulation resistance .
The insulation resistance of the photo-crosslinkable resin composition of the present invention can be represented by a dielectric constant when the coating thickness of the photo-crosslinkable resin composition is 2.0 to 4.0 占 퐉. When the dielectric constant is 3.5 or less, the insulation resistance is preferable.
In addition, the light transmittance of the insulating film according to the present invention can be expressed by a light transmittance measured at a wavelength of 550 nm and a coating thickness of the photocurable resin composition is 2.0 to 4.0 m, and is preferable as an insulating film when the light transmittance is 90% or more. If the light transmittance is lower than 90% under the above conditions, there is a problem in using it as a material for back-illuminated organic light emitting diodes.
The present invention also includes the rights relating to the organic light emitting element having the above-described insulating film. The method of manufacturing the organic light emitting device is not particularly limited, and examples of the method are as follows.
The method of manufacturing the organic light emitting device includes patterning a photoresist on a transparent substrate on which a transparent electrode such as ITO is deposited through patterning, exposure, development, etching, peeling, and forming an insulating film by the above- And then forming a barrier rib again on the insulating film pattern. Thereafter, an organic thin film is deposited in the order of an electron injection layer, an electron transporting layer, a light emitting layer, a hole transporting layer, and a hole injecting layer, and a metal electrode layer is deposited thereon. Finally, after sealing through the sealing material, the module can be assembled to manufacture an organic light emitting device.
When the composition comprising the alkali-soluble resin, the unsaturated ethylenic monomer, the photopolymerization initiator and the liquid-repellent polymer including the fluoroalkyl acrylate according to the present invention is dispersed in a certain amount of solvent, the photocurable resin composition according to one embodiment of the present invention Can be obtained. The photocurable resin composition of the present invention has good solubility in an alkaline developer. When light is irradiated, a composition containing an alkali soluble material other than the crosslinked portion, that is, a polyamic acid resin, is dissolved and removed. Due to such changes in solubility due to light irradiation, the non-exposed portion of the photoconductive resin composition of the present invention is developed.
That is, the photo-crosslinkable resin composition according to the present invention exhibits insolubility or poor solubility in an alkaline developer when exposed to light by a photopolymerization initiator, an alkali-soluble resin and an unsaturated ethylenic monomer, Is a negative type resist exhibiting a property of dissolving in an alkali developing solution.
Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are for illustrative purposes only, and the present invention is not limited to these examples. Further, it is intended that the present invention covers the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
< Example 1>
1-1: Preparation of alkali-soluble resin
743.87 g of propylene glycol monomethyl ether acetate (PGMEA) was charged as a first solvent while passing nitrogen through a 2-liter double-jacket flask equipped with a stirrer, a nitrogen injection device, a dropping funnel and a temperature controller, And 91.565 g (0.25 mol) of Bis-AP-AF as a diamine was completely dissolved therein. Thereafter, 111.0625 g (0.25 mol) of 6FDA as an aromatic dianhydride was added thereto. The mixture was stirred at 23 < 0 > C for 30 minutes to completely dissolve 6FDA. At this time, the concentration of the solid content was 21% by weight, and the polyamic acid resin of the following formula 1-1 formed by condensation polymerization was obtained at 23 캜 with a viscosity of 198 cps.
[Formula 1-1]
In the above formula 1-1, n is 34.
1-2: Photogenerating Resin composition manufacturing
80% by weight of the polyamic acid resin (at room temperature viscosity of 198 cps) obtained in Example 1-1 as an alkali-soluble resin, 2% by weight of an ethylene glycol (metha) acrylate (KAYARAD PEG400DA, NIPPON KAYAKU CO.) As an unsaturated ethylenic monomer, (OPTOACE 占 manufactured by Daikin Industries, Ltd.) containing 1% by weight of 2,2,2-trifluoroethyl methacrylate (MEHQ100) as a photopolymerization initiator, LTD.) And 0.15% by weight of a silicone additive (BYK307) used as a leveling agent as other additives were mixed and stirred at 23 캜 for 3 hours to prepare a photocurable resin composition.
< Example 2>
2-1: Production of alkali-soluble resin
In the same manner as in Example 1-1, 91.565 g (0.25 mol) of Bis-AP-AF as an aromatic diamine was completely dissolved. Then, 111.0625 g (0.25 mol) of 6FDA as an aromatic dianhydride was added and stirred at 23 DEG C for 20 minutes to completely dissolve 6FDA. To this was added 39.55 g (0.5 mol) of pyridine to aid in the extraction to a stable state through some chemical imidization, and the mixture was stirred at 80 ° C for 15 minutes, and the stirred mixture was poured into 3 L of water to precipitate. The precipitated solid was filtered and pulverized to fine powder and dried in a vacuum drying oven at 100 ° C. for 18 hours to obtain about 90 g of a polyamic acid resin solid powder having a weight average molecular weight of 49,800 g / mol).
[Formula 1-2]
In the above formula 1-2, n is 78.
2-2: Photogenerating Resin composition manufacturing
56% by weight of the polyamic acid resin (weight average molecular weight: 49,800 g / mol) obtained in the above Example 2-1 as an alkali-soluble resin, 56% by weight of an ethylene glycol (metha) acrylate (KAYARAD PEG400DA, NIPPON KAYAKU CO.) 35% by weight, 2,2,2-trifluoroethyl methacrylate (MEHQ100) as a photopolymerization initiator, 4% by weight of a silicone additive (BYK307) used as a leveling agent and 4% by weight of a liquid repellent polymer (OPTOACE ™ , DAIKIN Industries, LTD.) Containing fluoroalkyl acrylate, 1% by weight, and the mixture was stirred at 23 캜 for 3 hours to prepare a photocurable resin composition.
< Comparative Example 1>
1-1: Preparation of alkali-soluble resin
The procedure of Example 1-1 was repeated to produce an alkali-soluble resin.
1-2: Photogenerating Resin composition manufacturing
81% by weight of the polyamic acid resin (at room temperature viscosity of 198 cps) obtained in the above Comparative Example 1-1 as an alkali-soluble resin, 2 g of ethylene glycol (metha) acrylate (KAYARAD PEG400DA, NIPPON KAYAKU CO.) As an unsaturated ethylenic monomer, 1% by weight of 2,2,2-trifluoroethylmethacrylate (MEHQ100) as a photopolymerization initiator and 0.15% by weight of a silicone additive (BYK307) used as a leveling agent as an additive were mixed, Lt; RTI ID = 0.0 > 23 C < / RTI > to prepare a photocurable resin composition.
< Comparative Example 2>
2-1: Production of alkali-soluble resin
A polyamic acid resin was prepared in the same manner as in Example 1-1, except that 91.57 g (0.25 mol) of Bis-AP-AF as an aromatic diamine was completely dissolved and then 6FDA as a dianhydride was dissolved in (0.213 mol) slightly lower than the molar ratio and stirred at 23 DEG C for 30 minutes. At this time, a polyamic acid resin having a viscosity of 43 cps at 23 캜 was obtained. Then, acetic anhydride and pyridine were added to the polyamic acid resin under the same conditions as in Example 2-1 as a chemical imidizing agent. The stirred mixture was poured into 3 L of water to precipitate. The precipitated solids were filtered and pulverized to fine powder and dried in a vacuum drying oven at 100 ° C. for 19 hours to obtain about 180 g of resin solid powder (weight average molecular weight of polyamic acid resin: 20,000 g / mol) Respectively.
2-2: Photogenerating Resin composition manufacturing
The polyamic acid resin obtained in Comparative Example 2-1 was used as the alkali-soluble resin in the same manner as in Comparative Example 1-2.
81% by weight of the polyamic acid resin (at room temperature viscosity of 198 cps) obtained in the above Comparative Example 2-1 as an alkali-soluble resin, 2 g of ethylene glycol (metha) acrylate (KAYARAD PEG400DA, NIPPON KAYAKU CO.) As an unsaturated ethylenic monomer, 1% by weight of 2,2,2-trifluoroethylmethacrylate (MEHQ100) as a photopolymerization initiator and 0.15% by weight of a silicone additive (BYK307) used as a leveling agent as an additive were mixed, Lt; RTI ID = 0.0 > 23 C < / RTI > to prepare a photocurable resin composition.
< Comparative Example 3>
3-1: Production of alkali-soluble resin
91.565 g (0.25 mol) of TFDB (2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl) having no hydroxy group as an aromatic diamine was polymerized in the same manner as in Example 1-1, -AF, followed by addition of 111.0625 g (0.25 mol) of 6FDA as aromatic dianhydride and stirring at 23 DEG C for 30 minutes to completely dissolve 6FDA. At this time, the concentration of the solid content was 20 wt%, and then the resin formed by condensation polymerization was obtained at 23 DEG C with a viscosity of 40 cps.
3-2: Photogenerating Resin composition manufacturing
Using the alkali-soluble resin prepared in Comparative Example 3-1, a photocurable resin composition was prepared in the same manner and composition as in Example 1-2. 81% by weight of the polyamic acid resin (at room temperature viscosity of 198 cps) obtained in the above Comparative Example 3-1 as an alkali-soluble resin, 2 g of ethylene glycol (metha) acrylate (KAYARAD PEG400DA, NIPPON KAYAKU CO.) As an unsaturated ethylenic monomer, 1% by weight of 2,2,2-trifluoroethylmethacrylate (MEHQ100) as a photopolymerization initiator and 0.15% by weight of a silicone additive (BYK307) used as a leveling agent as an additive were mixed, Lt; RTI ID = 0.0 > 23 C < / RTI > to prepare a photocurable resin composition.
< Comparative Example 4>
(1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1,1-dihydroxyphenyl] propane was added to 88 wt% of the polyamic acid resin obtained in Example 1-1 as an alkali- 6% by weight of a sensitizer (1- [1- (4-hydroxyphenyl) ethyl] benzene) -1,2-naphthoquinonediazide- (OPTOACE ™ , DAIKIN Industries, LTD.) Containing 1.5% by weight of a fluoroalkyl acrylate and 1.5% by weight of 1,1-bis (4-hydroxyphenyl) .) As a leveling agent and 0.5 wt% of a silicone additive as a leveling agent were added to the mixture and stirred at 23 캜 for 2 hours to prepare a photocurable resin composition.
< Comparative Example 5>
To a 12 wt% polyamic acid resin prepared in Example 2-1, a diazide photosensitive compound ((1- [1- (4-hydroxyphenyl) isopropyl] -4- [ , 6 wt% of a solvent (propylene glycol monomethyl ether acetate), 76 wt% of a sensitizer (1- [1- (2-hydroxyphenyl) ethyl] benzenesulfonyl) -1,2-naphthoquinonediazide- (OPTOACE 占 ) containing 1.5% by weight of a fluoroalkyl acrylate and 1.5% by weight of a poly (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] , DAIKIN Industries, LTD.) And 0.5% by weight of a silicone additive as a leveling agent for another additive, and stirred at 23 캜 for 2 hours to prepare a photocurable resin composition.
The formation and evaluation of the insulating film using the photoconductive resin composition prepared according to Examples 1 to 2 and Comparative Examples 1 to 5 were carried out by the methods of Test Examples 1 to 6 and the results are shown in Table 1 below.
< Test Example One: Contact angle Measurement>
The photo-crosslinkable resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 5 were spin-coated on ITO substrate to a thickness of 3.0 탆. Thereafter, the substrate was preliminarily heat-treated for 100 seconds on a hot plate at 100 ° C to be dried to form a coating film having a thickness of 3.0 ± 0.05 μm. The substrate was irradiated with ultraviolet rays in the range of 100 mJ / cm 2 in the whole exposure, developed in 2.38% TMAH alkali developing solution for 80 seconds, and rinsed for 20 seconds. The PGMEA contact angle of the coating remained on the front surface of the Kruss DSA100 instrument was measured after post-baking for 60 minutes on a hot plate at 230 ° C.
< Test Example 2: Resolution measurement>
The photocurable resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 5 were spin-coated on ITO substrate to a thickness of 3.0 탆, pre-heat-treated for 100 seconds on a hot plate at 100 캜, 0.0 > 0.05 < / RTI > The substrate was irradiated with ultraviolet rays in a range of 100 mJ / cm 2 using a photomask for each pattern size (2 to 100 탆), developed with a 2.38% TMAH alkali developer for 80 seconds, and rinsed for 20 seconds. Thereafter, the patterned portion was left to form a circuit, and the pattern size of the obtained coating film was observed with an optical microscope.
< Test Example 3: Measurement of transmittance>
Using the photocrosslinkable resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 5, the coating composition was preliminarily heat-treated on a plate of a coating machine without being patterned. Then, the transmittance was measured by UV-Transmittance at 550 nm, and after heat treatment at 250 ° C for 1 hour without bleaching, the transmittance was measured to confirm the presence or absence of yellowing due to the heat treatment.
< Test Example 4: Measurement of dielectric constant>
The photocrosslinkable resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 5 were each spin coated on ITO substrate to a thickness of 3.0 탆. Thereafter, the film was dried by a preliminary heat treatment for 100 seconds on a hot plate at 100 占 폚 to form a coating film having a thickness of 3.0 占 0.05 占 퐉. The substrate was irradiated with ultraviolet rays in the range of 100 mJ / cm 2 using a photomask, developed with 2.38% TMAH alkali developer for 60 seconds, and rinsed for 40 seconds. Then, the substrate was heated on a hot plate at 230 DEG C for 1 hour to form an insulating film having a final thickness of 2.4 mu m. A metal electrode (AI) was deposited on the formed insulating film to a thickness of 2,000 Å (Thermal Evaporator Model E306), and dielectric constant was measured using a Precision Impedance Analyzer (Model: 4294A, HP).
< Test Example 5: Measurement of outgas>
The photocurable resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 5 were dried at 150 ° C for 5 hours in order to volatilize the solvent. Then, 0.5 mg of each sample was collected in a GC-MS vial, and the gas generated after standing in a furnace at 280 ° C. for 30 minutes was collected. This was measured with a Pyrolyze GC-MS to measure the total area of all peaks, and then the relative amount of outgas was compared based on the peak area of Example 2.
< Test Example 6: Residue Measurement of occurrence>
A pattern was formed in the same manner as in the resolution measurement of Test Example 2, and it was observed with a scanning electron microscope (SEM) whether or not the pattern could be developed without residue in an 8 mu m pattern. The results are shown in the following Table 1, and it is indicated by "X" when there is no residue, "Δ" when there is a partial residue, and "○" when there is a residue. 1 shows an image of a resolution pattern measured using the photo-crosslinkable resin composition of Example 1. Fig.
(Relative area)
As shown in Table 1, the insulating films prepared from the compositions of Examples 1 and 2 were found to be equivalent to each other in terms of the residue generation, the light transmittance, the dielectric constant and the outgassing in comparison with Comparative Examples 1 to 5. Also, it was confirmed that the contact angles of propylene glycol monomethyl ether acetate (PGMEA) were more than 40 degrees (°) only in the compositions of Examples 1 and 2. As shown in FIG. 1, it was confirmed that no residue was generated at the interface between the exposed and unexposed portions. On the other hand, in Comparative Examples 1 and 2 in which fluoroalkyl acrylate-containing liquid repellent polymer was not contained, the contact angle was so small that it could not be measured. In Comparative Example 3 in which condensation polymerized monomer having no OH group was not developed, It was confirmed that the effect of increasing the contact angle can not be obtained even when the liquid detergent polymer containing fluoroalkyl acrylate is included in the composition in the photodegradable composition as in Comparative Examples 4 to 5. [
Claims (16)
The alkali-soluble resin (A) is a polyamic acid containing a repeating unit represented by the following formula (2)
Wherein the liquid repellent polymer (D) comprises a fluoroalkyl acrylate represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
A is a fluoroalkyl group (Rf) or a perfluoropolyether group (PFPE)
B is H, CH 3 or halogen;
(2)
In Formula 2,
R 1 and R 2 are the same or different and each independently is a divalent to octavalent organic group having at least 2 carbon atoms,
R 3 and R 4 are the same or different and each independently an organic group of 1 to 12 carbon atoms containing a hydroxy group, hydrogen or halogen,
x is an integer of 0 to 2, y is an integer of 0 to 4, x + y > 0, z is an integer of 0 to 2,
n is an integer of 10 to 200;
Wherein R 1 and R 2 in Formula 2 are the same or different from each other and each independently a diphenyl group containing a fluoroalkyl group having 2 to 8 carbon atoms.
5 to 80 parts by weight of an unsaturated ethylenic monomer, 0.5 to 10 parts by weight of a photopolymerization initiator, and 0.5 to 10 parts by weight of a liquid repellent polymer, based on 100 parts by weight of the alkali-soluble resin.
Wherein the alkali-soluble resin is prepared by polymerizing an aromatic diamine and an aromatic dianhydride in a first solvent.
The alkali-soluble resin is produced by polymerizing an aromatic diamine and an aromatic dianhydride in a first solvent to prepare a polyamic acid resin, or adding the obtained polyamic acid resin to a second solvent, followed by filtration and drying Based on the total weight of the photopolymerizable composition.
The aromatic diamine may be selected from the group consisting of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis-AP- ] Propane (6HMDA), 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB), 3,3'- 4,4'-diaminobiphenyl (3,3'-TFDB), 4,4'-bis (3-aminophenoxy) diphenyl sulfone (DBSDA), bis Bis (4-aminophenoxy) benzene (APB-134), 1,3-bis (3-aminophenoxy) benzene (4-aminophenoxy) phenyl] hexafluoropropane (4-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), 2,2'-bis [ -BDAF) and oxydianiline (ODA). ≪ / RTI >
The aromatic dianhydride may be at least one selected from the group consisting of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydrate (6FDA), 4- (2,5-dioxotetrahydrofuran- , 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), 4,4 '- (4,4'-isopropylidene diphenoxy) bis (phthalic anhydride (4,4'-oxydiphthalic dianhydride) (ODPA) and 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride (BPDA) Wherein the photo-crosslinkable resin composition is at least one selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol.
The first solvent may be at least one selected from the group consisting of m-crossover, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) Ether acetate (PGMEA) and diethyl acetate. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the second solvent is at least one selected from water, alcohols, ethers, and ketones.
Wherein the alkali-soluble resin has a weight average molecular weight of 10,000 to 40,000 g / mol.
Wherein the unsaturated ethylenic monomer is an acrylic monomer having at least one unsaturated ethylene bond.
Wherein the insulating film has a light transmittance of 90% or more.
Wherein the insulating film has a dielectric constant of 3.5 or less.
Wherein the insulating film has a contact angle with respect to propylene glycol monomethyl ether acetate (PGMEA) of 40 degrees or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10146129B2 (en) | 2016-11-25 | 2018-12-04 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, black pixel defining layer using the same and display device |
| CN112194793A (en) * | 2019-07-08 | 2021-01-08 | Jnc株式会社 | Polyamic acid composition |
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| US10896942B2 (en) * | 2015-03-11 | 2021-01-19 | Toray Industries, Inc. | Organic EL display device and method for manufacturing same |
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| CN101081951B (en) * | 2006-05-30 | 2010-06-16 | 奇美实业股份有限公司 | Ink component for micro color-patch pattern defect correction of colorful filter |
| KR101121038B1 (en) * | 2008-07-01 | 2012-03-15 | 주식회사 엘지화학 | Photoresist resin composition containing a number of photo-initiators, transparent thin film layer and liquid crystal display using the same |
| KR101443293B1 (en) * | 2009-10-15 | 2014-09-19 | 주식회사 엘지화학 | Alkali developable photosensitive resin composition and dry film manufactured by the same |
| KR101737370B1 (en) * | 2012-09-28 | 2017-05-18 | 후지필름 가부시키가이샤 | Photosensitive resin composition, method for producing cured film, cured film, organic el display device, and liquid crystal display device |
| KR20140073759A (en) * | 2012-12-07 | 2014-06-17 | 코오롱인더스트리 주식회사 | Photo-crosslinking resin composition, insulating film and oled formed by using the same |
| JP6332022B2 (en) * | 2012-12-20 | 2018-05-30 | 東レ株式会社 | Photosensitive resin composition, heat-resistant resin film manufacturing method, and display device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10146129B2 (en) | 2016-11-25 | 2018-12-04 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, black pixel defining layer using the same and display device |
| CN112194793A (en) * | 2019-07-08 | 2021-01-08 | Jnc株式会社 | Polyamic acid composition |
| CN112194793B (en) * | 2019-07-08 | 2024-04-26 | Jnc株式会社 | Polyamic acid composition |
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| TW201610568A (en) | 2016-03-16 |
| TWI566038B (en) | 2017-01-11 |
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