WO2013105813A2 - 전자소자용 절연재 - Google Patents
전자소자용 절연재 Download PDFInfo
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- WO2013105813A2 WO2013105813A2 PCT/KR2013/000247 KR2013000247W WO2013105813A2 WO 2013105813 A2 WO2013105813 A2 WO 2013105813A2 KR 2013000247 W KR2013000247 W KR 2013000247W WO 2013105813 A2 WO2013105813 A2 WO 2013105813A2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—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 H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/38—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes condensation products of aldehydes with amines or amides
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- C—CHEMISTRY; METALLURGY
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—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 H01B3/38 or H01B3/302
- H01B3/305—Polyamides or polyesteramides
Definitions
- Insulation material for electronic device is Insulation material for electronic device
- the present invention relates to an insulating material for an electronic device that can exhibit excellent physical properties and reliability while preventing damage to the electronic device due to the high temperature curing step of the insulating material.
- the polyimide resin has good flattening characteristics of the coating surface in addition to excellent electrical properties such as high heat resistance, excellent mechanical strength, low dielectric constant, and high insulation, and has a very low content of impurities that degrade the reliability of the device.
- an insulating material such as an insulating film containing the same has recently been extended to reach various electronic devices.
- polyimide resins themselves usually exhibit low solubility in organic solvents, and N-methyl-2-pyridone (NMP; boiling point: about 202 ° C.) or gammabutyrolactone (GBL; boiling point: about 204 ° C.). Some solubility can only be shown for organic solvents having a high boiling point such as).
- a method of polymerizing to obtain a polyimide precursor solution, for example, a polyamic acid ester solution, and the like, and applying the same to a substrate and then imidizing and curing the polyimide precursor by high temperature heat treatment.
- NMP N-methyl-2-pyridone
- the present invention does not require a high temperature curing step in the formation process to provide damage to the electronic device, while providing an insulating material for an electronic device that can exhibit excellent physical properties.
- the present invention comprises a soluble polyimide resin comprising a repeating unit of the formula (1), after curing at a temperature of about 250 ° C or less, at least about 70%
- An insulating material for an electronic device which exhibits an imidization ratio and comprises a low boiling point solvent having a boiling point of 130 to 180 ° C. as a residual solvent, is provided.
- p is an integer of 2 to 500
- X is a tetravalent organic group
- Y is a divalent organic group having at least one hydroxy group or carboxyl group.
- the imidation ratio is formed on the substrate a resin composition comprising a soluble polyimide resin and a low boiling point solvent, prebaked at about 110 to 130 ° C, hard bake at about 220 to 250 ° C Can be measured after.
- the imidation ratio is about 1350-1400 cm " of the IR spectrum after forming a resin composition comprising a soluble polyimide resin and a low boiling point solvent on a substrate and heat-treating it at a temperature of about 300 ° C.
- the integral intensity of the CN band represented by 1 or about 1550 to 1650 crrf 1 is 100%, it may be expressed as a relative integral intensity ratio of the CN band after hard baking at about 220 to 250 ° C.
- the insulating material for an electronic device may include an amine catalyst having a boiling point of about 60 to 120 ° C. as a residual catalyst, and the amine catalyst is ⁇ , ⁇ -diethylmethylamine, ⁇ , ⁇ -dimethylisopropyl Amine, ⁇ -methylpyridine ( ⁇ -
- It may include one or more selected from the group consisting of Methylpyrrolidine, pyriOlidine, and triethylamine.
- the amount of outgassing after curing of the insulating material may be about 4 ppm or less with respect to the total weight of the soluble polyimide resin, and the amount of residual catalyst during outgasing is about 0.5 ppm or less.
- the low boiling point solvent is diethylene glycol methylethyl ether, diethylene glycol dimethyl ether, diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxy propionate, ethyl 3-ethoxy Propionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclonucleanone and propylene glycol monomethyl ether acetate (PGMEA) may include one or more selected from the group consisting of.
- the amount of outgassing after curing of the insulating material may be about 4 ppm or less with respect to the total weight of the soluble polyimide resin, and the amount of residual solvent in the outgasing is about 0.1 ppm or less.
- Y in Chemical Formula 1 may be at least one selected from the group consisting of:
- X in Formula 1 may be at least one selected from the group consisting of:
- the soluble poly The glass transition temperature may be about 150 to 400 ° C., and the weight average molecular weight may be about 1,000 to 500,000.
- the insulating material for an electronic device may be formed on various substrates such as a glass substrate or a metal substrate, but may be appropriately formed on a plastic substrate which is particularly susceptible to heat, and is particularly susceptible to OLED, LCD or semiconductor devices, particularly heat. It can also be preferably applied as an insulating material of an OLED element.
- the insulating material for an electronic device according to the present invention is less than 300 ° C, for example 250 ° C on a substrate, without the need to proceed to the high temperature curing process previously required for conversion to polyimide resin or removal of solvents or catalysts, etc. Even if only a low heat treatment process is performed at the following temperature, high imidization rate and excellent physical properties can be exhibited. Effective removal can also minimize the amount of residual solvent and residual catalyst. Therefore, by using the insulating material of the present invention, the high temperature curing process and the like are not necessary, and thus the electrical property change or damage of the electronic device can be suppressed.
- the insulating material is very preferable as an insulating material such as an OLED device which is susceptible to heat. Can be applied.
- the term "insulation material for electronic devices” may refer to any insulating material used in various electronic devices such as E-deo, LCD, or semiconductor devices. Examples of such an insulating material include an insulating film, an insulating film, a photosensitive film, a photosensitive film, a substrate, or a partition wall used in various electronic devices, and not limited to any material that does not exhibit conductivity. Can be included. In addition, the form of the "insulation material for electronic devices” may also take various forms, not limited to a specific form such as a thin film or a film.
- a soluble polyimide resin comprising a repeating unit of the formula (1), after curing at a temperature of about 250 ° C or less, exhibits an imidization ratio of about 70% or more, boiling point about 130
- An insulating material for an electronic device comprising a low boiling point solvent, which is from about 180 ° C. as a residual solvent, is provided:
- p is an integer of 2 to 500
- X is a tetravalent organic group
- Y is a divalent organic group having at least one hydroxy group or carboxyl group.
- the insulating material for an electronic device described above basically includes a soluble polyimide resin having a repeating unit represented by Chemical Formula 1.
- soluble polyimide resins contain functional groups Y having a hydroxy group or a carboxyl group in the repeating unit, and exhibit excellent solubility in a wider range of organic solvents, such as low boiling point solvents such as PGMEA (boiling point: about 145 ° C.). Can be. Therefore, by using such a soluble polyimide resin, by forming a solution of the soluble polyimide resin itself on the substrate and heat treatment without the need to use a polyimide precursor solution such as a polyamic acid ester solution by easily removing the low boiling point solvent and the like Insulation material for an electronic device can be formed.
- the soluble polyimide resin can be obtained by polymerizing a diamine compound having a hydroxy group or a carboxyl group and a dianhydride in the presence of a predetermined low boiling point amine catalyst, in particular, a predetermined amine It can be provided to have a high imidization rate even under low polymerization temperature and / or curing temperature through the use of a system catalyst and the like. Therefore, in one embodiment, the insulating material for an electronic device is a heat treatment or curing process at a low temperature of less than about 30C C, for example, about 25CTC or less after forming the resin composition including the soluble polyimide resin and the low boiling point solvent on a substrate. Even if only to proceed, at least about 70%, or at least about 80%, or at least about 90%, black may be provided to have a high imidization rate of about 90 to 99%.
- the soluble polyimide resin may be formed of an insulating material by polymerization, coating and curing on a substrate in the presence of a low boiling point amine catalyst while being dissolved in a low boiling point solvent due to excellent solubility and curing properties. For this reason, during the formation of the insulating material, a heat treatment or curing process for removing residual solvent and / or catalyst may also proceed to a lower temperature of less than about 300 ° C., for example, about 250 ° C. or less.
- the insulating material for an electronic device of one embodiment has a high imidation ratio of about 70% or more, even when provided by a heat treatment or curing process at a temperature lower than about 300 ° C., for example, about 250 ° C. or less.
- the low boiling point solvent and the catalyst can be effectively removed by such a low temperature heat treatment process. Therefore, the residual amount of the low boiling point solvent and the catalyst which can be included as the residual solvent and the residual catalyst in the insulating material can be minimized, and the insulating material can exhibit more excellent physical properties. For this reason, when the insulating material of one embodiment is applied, a high temperature heat treatment or hardening process, for example, a heat treatment or hardening process of about 300 ° C.
- the insulating material for an electronic device of one embodiment can be substantially omitted, such as a high temperature process during the formation process, it is possible to suppress the characteristics of the electronic device change or damage to the electronic device according to the high temperature process, excellent physical properties It is possible to provide an insulating material having. For example, when the high temperature process is performed, the characteristics of the electronic device may be changed or the electronic device may be damaged if the electrical property of the TFT is changed, or when the insulation material for the electronic device of one embodiment is applied. This high temperature process can be omitted to substantially prevent any alteration or damage to the properties of these devices.
- the insulating material of the embodiment can be preferably applied to electronic devices having heat-vulnerable properties, particularly organic materials such as OLED devices, and on plastic substrates having heat-vulnerable properties as well as glass or metal substrates. It is also preferably applied to exhibit excellent physical properties. Therefore, the insulating material of one embodiment overcomes the technical limitations of the conventional polyimide insulating material, and can be very preferably applied as an insulating material of various electronic devices. It will be described in more detail for the "below, one embodiment the electronic device for the insulating material, the physical properties and methods for their preparation.
- the imidation ratio is a substrate Forming a resin composition comprising the soluble polyimide resin and a low boiling point solvent on the prebaking at about 110 to 130 ° C, may be measured after hard baking at about 220 to 25 C.
- the imidation rate is about 1-5 minutes at about 120 ° C., for example, about 4 minutes and about 0.5-2 hours at about 230 ° C., respectively. For example after about 1 hour.
- the insulating material of one embodiment is about 70% or more, or about 80% or more, or about 90% It may have a high imidation ratio of about 90% or more, or about 90% to 99%, and may effectively remove a low boiling point solvent, thereby minimizing the amount of residual solvent. It has a characteristic that can be omitted, and even in this case, it can exhibit excellent physical properties according to high imidation ratio.
- the imidization rate can be analyzed from the IR spectrum.
- the imidation ratio is obtained by forming a resin composition comprising a soluble polyimide resin and a low boiling point solvent on a substrate and heat-treating to a temperature of about 300 ° C.
- the integral intensity of the CN band afterwards can be measured by the ratio with respect to the integral intensity which becomes the following reference
- the imidization rate is about 60% It was found not to be.
- the insulating material soluble polyimide resin After forming a composition comprising a low boiling point solvent and the like on the substrate, even if only the curing process under the low temperature described above may be about 90% imidization rate, the high temperature curing process of about 30CTC or more can be omitted It is confirmed that even if only a low temperature heat treatment or curing process is performed, high imidization ratio and excellent physical properties can be exhibited.
- the insulating material for an electronic device of the embodiment described above may include an amine catalyst having a boiling point of about 60 to 120 ° C, or about 70 to 100 ° C, or about 80 to 9 C C as a residual catalyst, such an amine
- the catalyst consists of, for example, ⁇ , ⁇ -diethylmethylamine, ⁇ , ⁇ -dimethylisopropylamine, ⁇ -methylpyrrolidine, pyrrolidine, and triethylamine It may include one or more selected from the group. Among them, triethylamine having a boiling point of about 89 ° C. is used as an amine catalyst in consideration of low boiling point and effective removal of residual catalyst and catalytic activity for achieving high imidization ratio. It may include.
- the insulating material of the embodiment is heat-treated or cured (eg, prebaked at about 110 to 130 ° C and hardbaked at about 220 to 250 ° C) at a low temperature of about 250 ° C or less, and then out
- the amount of gasing generated may be about 4 ppm or less, for example, about 0 to 3 ppm and black to about 0.1 to 2.5 ppm with respect to the total weight of the soluble polyimide resin, and the amount of residual catalyst in such outgassing is about 0.5 ppm or less. For example, it may be only about 0 to 0.5ppm, or about 0.05 to 0.3ppm.
- the soluble polyimide resin included in the insulating material of one embodiment may be polymerized to have a high imidization ratio in the presence of a specific amine catalyst, that is, the amine catalyst having a low boiling point described above. Therefore, the insulating material of one embodiment obtained by applying a solution containing such a soluble polyimide resin, a low boiling point solvent, and the like, and performing a heat treatment or a curing process may include such a specific amine catalyst as a residual catalyst. However, since the residual catalyst of such a specific amine catalyst has a low boiling point, almost all or substantially completely during the heat treatment or curing process at a low temperature of about 25 C C or less. Can be removed.
- the insulating material of one embodiment may not only be a trace amount of the residual catalyst amount substantially below or equivalent to the detection limit, but also significantly reduce the total outgassing generation amount including the residual catalyst amount itself.
- the insulating material of one embodiment may exhibit more excellent physical properties even if the high temperature heat treatment or curing process is omitted, and it is possible to reduce the deterioration of the device characteristics due to the outgassing.
- the insulating material for an electronic device of one embodiment may include a low boiling point solvent having a boiling point of about 130 to 180 ° C, or about 140 to 160 ° C as a residual solvent, such a low boiling point solvent, for example , Diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , dipropylene glycol dimethyl ether, methyl 3- methoxy propionate ⁇ ethyl 3- ethoxy propionate, propylene glycol methyl ether pro It may comprise one or more low boiling point polar solvents selected from the group consisting of cypionate, dipropylene glycol dimethyl ether, cyclonucleanone and propylene glycol monomethyl ether acetate (PGMEA).
- a low boiling point solvent having a boiling point of about 130 to 180 ° C, or about 140 to 160 ° C as a residual solvent
- a low boiling point solvent for example , Diethylene glycol
- propylene glycol monomethyl ether acetate having a boiling point of about 145 ° C. is used as a low boiling point solvent in consideration of low boiling point and thus effective residual solvent removal and high conversion to soluble polyimide resin. It can be used as a residual solvent.
- the insulating material of the embodiment is heat-treated or cured (eg, prebaked at about 110 to 130 ° C, hardbaked at about 220 to 250 ° C) at a low temperature of about 250 ° C or less, and then out
- the amount of gasing generated may be about 4 ppm or less, for example, about 0 to 3 ppm and black to about 0.1 to 2.5 ppm based on the total weight of the soluble polyimide resin, and the amount of residual solvent in such outgassing is about 0.1 ppm or less, For example, it may be only about 0 to 0.5 ppm, or about 0.01 to 0.03 ppm. In one embodiment, the residual solvent amount may fall short of the detection limit.
- Soluble polyimide resin included in the insulating material of one embodiment unlike the conventional polyimide resin, even for a polar solvent having a low boiling point described above, Excellent solubility can be exhibited. Therefore, the insulating material of one embodiment may be obtained by polymerizing a soluble polyimide resin in such a low boiling point solvent, applying a resin composition containing such a thickening solution to a substrate, and performing a heat treatment or a curing process. Therefore, the insulating material of one embodiment may include such a low boiling point solvent as the residual solvent. However, since these residual solvents have a low boiling point, almost all black may be substantially completely removed during the heat treatment or curing process at a low temperature of about 250 ° C. or less.
- the insulating material of one embodiment may not only have a residual amount of the solvent substantially lower than or equivalent to the detection limit, but also lower the total outgassing amount itself.
- the insulating material of one embodiment may exhibit excellent physical properties even if the high temperature heat treatment or curing process is omitted, and further reduce the deterioration of the device characteristics due to the outgassing and the residual solvent.
- the soluble polyimide resin includes a repeating unit of Formula 1 as a main repeating unit, which may include a divalent functional group of Y having a hydroxy group or a carboxyl group. Due to the presence of such functional groups, the soluble polyimide resin can exhibit excellent solubility in low boiling point polar solvents, and can exhibit excellent imidization rate even at low temperature polymerization and curing under a predetermined amine catalyst.
- Y include a divalent functional group having a phenolic hydroxy group or a carboxyl group, for example a divalent aromatic functional group selected from the group consisting of:
- the repeating unit of Formula 1 of the soluble polyimide resin may include a tetravalent functional group X derived from dianhydride.
- X include 4 selected from the group consisting of Are aromatic or aliphatic functional groups:
- the above-mentioned soluble polyimide resin may be a single polymer or a co-polymer including only one or more of the repeating units of the formula (1), but as a copolymer further comprising a repeating unit of a different kind from the formula (1) May be
- the soluble polyimide resin may further include a polyimide repeating unit represented by the following Formula 1.
- the soluble poly already taking into consideration the solubility or cured properties for the low-boiling-point solvent of the imide resin, a repeating unit represented by the above formula (1) from about 50 mole 0/0 or more, or about 60 mole 0/0 or more, or from about 70 mol% or more, or at least about 80 mol%, the black can comprise from about 90 mole 0/0 or more:
- X and p are as defined in Formula 1
- Y ' represents a divalent aliphatic or aromatic organic group having no hydroxy group or carboxyl group.
- examples of Y ′ are well known to those skilled in the art and include, for example, one selected from the group consisting of
- the glass transition temperature of the soluble polyimide resin may be about 150 to 40C C
- the weight average molecular weight may be about 1,000 to 500,000
- black about 5,000 to 100,000.
- the above-described insulating material for an electronic device the resin composition containing the soluble polyimide resin, for example, the photosensitive resin composition or printing ink composition containing the soluble polyimide resin is applied to the substrate, and the heat treatment or curing process It can be formed to proceed.
- the insulating material according to the conventional components of the photosensitive resin composition or the ink composition for printing Additional additives or crosslinking agents may be further included.
- the insulating material may further include a residual photoacid generator, a photoactive compound and / or a crosslinking agent, and may include a crosslinking structure derived from such a crosslinking agent and a soluble polyimide resin.
- various additives derived from conventional components of the photosensitive resin composition or the ink composition for printing may be further included.
- the insulating material for an electronic device described above may exhibit a high imidization rate, a low residual catalyst amount, a low residual solvent amount, a low outgassing amount, and the like, even when the high temperature heat treatment or curing process of about 30C C or more is omitted. . Therefore, such an insulating material can be applied as an insulating material of various electronic devices such as OLED, LCD, or semiconductor devices, and is particularly preferably applied to electronic devices having heat-vulnerable properties, including organic materials such as E-de0 devices. Can be represented.
- the insulating material of one embodiment may be formed on a glass substrate or a metal substrate, and may also be preferably formed on a relatively heat-sensitive plastic substrate, and various types of insulating materials included in electronic devices, for example It can be suitably applied as an insulating film, an insulating film, a photosensitive film, a photosensitive film, a substrate or a partition.
- the above-described insulating material for an electronic device is a low boiling point solvent, in the presence of a predetermined low boiling point amine-based catalyst, the diamine containing a hydroxy group or a carboxyl group and the dione hydride polymerized to obtain the above-mentioned soluble polyimide resin, solubility
- the solution in which the polyimide resin is dissolved in a low boiling point solvent may be applied onto a substrate and then heat-treated (or cured) at a low temperature of about 250 ° C. or less.
- a manufacturing process after obtaining a soluble polyimide resin having a high imidation ratio by performing a polymerization process using a predetermined low boiling point amine catalyst, the solution thereof is applied to a substrate and a low temperature heat treatment (or curing) process is performed. By advancing, an insulating material is formed.
- a low temperature heat treatment (or curing) process By advancing, an insulating material is formed.
- both the amine catalyst and the solvent have a boiling point lower than the temperature of the heat treatment (or curing) process, in this low temperature heat treatment (or curing) process Almost all or substantially totally removable, the soluble polyimide resin can be removed from immediately after polymerization to the formation of an insulating material with the use of a specific amine catalyst.
- a high imidation rate of 70% or more can be shown.
- the high temperature heat treatment or curing process of about 300 ° C or more is omitted, and only the low temperature heat treatment or curing process of about 250 ° C or less proceeds after the solution of the soluble polyimide resin is applied onto the substrate, high imide
- an insulating material for an electronic device of one embodiment exhibiting a high fluorescence rate, a low residual solvent amount and a low residual catalyst amount, and thus excellent physical properties can be obtained.
- the above-mentioned soluble plimide resin is produced by combining diamine containing hydroxy group or carboxyl group and dianhydride in the presence of a predetermined low boiling point amine catalyst in a low boiling point solvent.
- the low boiling point organic solvent may use a polar organic solvent having a boiling point of about 130 to 18 CTC, or about 140 to 160 ° C, examples thereof include diethylene glycol methylethyl ether, diethylene glycol dimethyl ether, diethylene glycol di Ethyl ether, dipropylene glycol dimethyl ether, methyl 3- methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone or propylene glycol monomethyl Ether acetate (PGMEA), and the like.
- various polar organic solvents having the above-mentioned boiling range can be used, and two or more kinds of mixed solvents selected from them can be used.
- the conversion rate may not be reduced due to insufficient energy for making a polyimide. Also, if the boiling point of the solvent exceeds 180 ° C, a heat treatment for forming an insulating material ( Or curing) may not remove the residual solvent properly.
- the low boiling point solvent is about 20 to 2000 parts by weight, or about 100 to about 100 parts by weight of the total monomers including diamine and dianhydride 1000 parts by weight, black may be used in about 200 to 400 parts by weight.
- the content of the solvent is too low, it may not be possible to dissolve each monomer or soluble polyimide resin sufficiently, and when the content of the solvent is too high, a sufficient thickness when applying a solution of the soluble polyimide resin to the substrate after polymerization It may not be possible to form a coating film.
- an amine catalyst having a boiling point of about 60 to 12 CTC, or about 70 to iocrc, or about 80 to 9 rc can be used. If the boiling point of the catalyst is excessively high, the residual catalyst may not be properly removed in the heat treatment (or curing) process for the formation of the insulating material, and may cause side reactions, which is not appropriate.
- the low boiling point amine catalyst a catalyst capable of effective imidization at a low temperature and easy removal after reaction is used.
- the amine catalyst include N, N-diethylmethylamine, ⁇ , ⁇ - And a catalyst selected from the group consisting of dimethylisopropylamine, N-methylpyrralidine, pyrrolidine and triethylamine.
- Such a catalyst may be used in an amount of about 0.5 to 30 parts by weight, or about 2 to 20 parts by weight, or about 5 to 10 parts by weight, based on 100 parts by weight of the total monomers including the diamine and dianhydride.
- the content of the catalyst is too low, the conversion rate to the polyimide resin may drop, and when the catalyst content is too high, the residual catalyst may not be properly removed and may cause side reactions.
- diamines having a hydride group or a carboxyl group, respectively, and ordinary dianhydrides can be used as the monomers of the diamine and dianhydride for obtaining the above-mentioned soluble polyimide resin.
- dianhydride examples include pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3'3' ⁇ 4,4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'- Diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) nucleofluoroisopropylidene dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydrides, 3,3 ' ⁇ 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-nuxafluoroisopropylidenediphthalic anhydride, 3,3',
- diamines having a divalent organic group containing a phenolic hydroxyl group carboxyl group or a hydroxyl group, such as a divalent organic group derived from 3,5-diaminobenzoic acid Solubility through the polymerization of these diamines and dianhydrides
- a polyimide resin By preparing a polyimide resin, it becomes possible to prepare a soluble polyimide resin having excellent solubility even in the low boiling point solvent and the like described above.
- a solution of the soluble polyimide resin is prepared on a substrate.
- the insulating material of one embodiment exhibiting a high imidation ratio can be formed.
- a soluble polyimide resin in the form of a copolymer further comprising additional repeating units, for example, repeating units of the general formula (1) described above a dian using additional diamines together with the diamine having a hydroxy group or a carboxyl group It may be copolymerized with hydride.
- the diamine which can be used is not specifically limited, Any diamine known to be usable for formation of a polyimide resin can be used.
- diamine examples include phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine , 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4 ' -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4.-methylene-bis (2-methylaniline), 4,4'-methylene -Bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4
- the polymerization of each monomer including the diamine and dianhydride described above may be carried out at a low temperature of about 120 to 200 ° C, or about 130 to 180 ° C, black is about 140 to 160 ° C.
- the conversion to the polyimide resin may be about 90% or more, for example, about 90 to 100%, and the amount of residual catalyst in the polymerized polyimide resin may be It may be about 0.001 to 0.1 weight 0 /. In the mid resin.
- the polymerization and the produced soluble polyimide resin has a high imidization ratio by itself in the above-described method, a further already without the need for increasing imidization rate high, of about 250 ° C or less temperature, or up to about 250 ° C of At a temperature of about 150 to 250 ° C, or a temperature of about 230 ° C or less, or a temperature of about 200 ° C or less, low silver curing may proceed to form an insulating material having a high imidation ratio.
- the said soluble polyimide resin can exhibit the outstanding solubility also about the low boiling point solvent mentioned above.
- a solution in which such a resin is dissolved in a low boiling point solvent for example, a photosensitive resin composition or an ink composition for printing in such a solution state is applied to a substrate,
- the heat treatment or curing process may be performed to form an insulating material for an electronic device.
- the photosensitive resin composition or the ink composition for printing may further include additional additives, crosslinking agents, photoactive compounds or photoacid generators, and the kinds of these components are as well known to those skilled in the art.
- the heat treatment or curing process is a temperature of about 250 ° C or less, or about
- Temperature of 150 to 250 ° C, black may be at a temperature of about 23 CTC or less; or at a temperature of about 200 ° C or less, and even with such a low temperature heat treatment or hardening process, an insulating material having a high imidization ratio or the like may be produced. Yes is as described above.
- the low boiling point solvent or the like may be effectively removed by such a low temperature heat treatment process, and thus the amount of residual solvent may be minimized.
- the heat treatment or curing process can be carried out in two stages, a prebaking process and a hardbaking process, wherein the prebaking process and the hardbaking process are each at about 110 to 130 ° C. and at about 220 to 250 ° C. Can proceed.
- a prebaking process and a hardbaking process wherein the prebaking process and the hardbaking process are each at about 110 to 130 ° C. and at about 220 to 250 ° C. Can proceed.
- Example 2 Low Temperature Polyimide Polymerization Example
- Each polymer solution prepared in each of Examples and Comparative Examples was spin-coated on a silicon wafer, followed by prebaking at 120 ° C. for 4 minutes, and 230 ° C. for 1 hour hard baking, respectively. After the progress, the imidation ratio was measured using FT-IR for each.
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- Polymers & Plastics (AREA)
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
Description
Claims
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CN201380003325.9A CN103843073B (zh) | 2012-01-13 | 2013-01-11 | 用于电子器件的绝缘材料 |
EP13735849.5A EP2804185A4 (en) | 2012-01-13 | 2013-01-11 | INSULATING MATERIAL FOR ELECTRONIC DEVICE |
US14/349,351 US20140296408A1 (en) | 2012-01-13 | 2013-01-11 | Insulation Material for Electronic Device |
JP2014540976A JP5825651B2 (ja) | 2012-01-13 | 2013-01-11 | 電子素子用絶縁材 |
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EP (1) | EP2804185A4 (ko) |
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CN109426074A (zh) * | 2017-08-22 | 2019-03-05 | 达兴材料股份有限公司 | 感光树脂组合物、感光树脂及电子装置 |
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JP2015218230A (ja) * | 2014-05-16 | 2015-12-07 | 株式会社リコー | 熱可塑性ポリイミド、熱可塑性ポリイミド発泡体、及びこれらの製造方法 |
JPWO2016103966A1 (ja) * | 2014-12-26 | 2017-11-02 | 特種東海製紙株式会社 | 絶縁紙 |
KR102429886B1 (ko) * | 2017-11-30 | 2022-08-04 | 엘지디스플레이 주식회사 | 유기발광 표시장치 |
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US4927736A (en) * | 1987-07-21 | 1990-05-22 | Hoechst Celanese Corporation | Hydroxy polyimides and high temperature positive photoresists therefrom |
JPH09272739A (ja) * | 1996-04-04 | 1997-10-21 | Sumitomo Bakelite Co Ltd | ポリイミド樹脂 |
US6790930B1 (en) * | 1999-10-06 | 2004-09-14 | Kaneka Corporation | Process for producing polyimide resin |
KR100732895B1 (ko) * | 1999-11-30 | 2007-06-27 | 닛산 가가쿠 고교 가부시키 가이샤 | 포지티브형 감광성 폴리이미드수지 조성물 |
US6451955B1 (en) * | 2000-09-28 | 2002-09-17 | Sumitomo Bakelite Company Limited | Method of making a polyimide in a low-boiling solvent |
KR101252875B1 (ko) * | 2005-01-21 | 2013-04-09 | 미츠비시 가스 가가쿠 가부시키가이샤 | 폴리이미드 수지, 폴리이미드 필름 및 폴리이미드 적층체 |
JP5212596B2 (ja) * | 2006-05-24 | 2013-06-19 | 日産化学工業株式会社 | 有機トランジスタ |
US20090184347A1 (en) * | 2006-05-24 | 2009-07-23 | Nissan Chemical Industries, Ltd. | Coating liquid for gate insulating film, gate insulating film and organic transistor |
US20100304291A1 (en) * | 2007-12-14 | 2010-12-02 | Kazuya Ebara | Production method of polyhydroxyimide and positive photosensitive resin composition containing polyhydroxyimide obtained by the production method |
JP5796712B2 (ja) * | 2009-04-23 | 2015-10-21 | 日産化学工業株式会社 | ポリヒドロキシイミドの製造方法 |
JP2011148955A (ja) * | 2010-01-25 | 2011-08-04 | Kaneka Corp | ポリイミドフィルムの製造方法及び該製造方法により得られたポリイミドフィルム |
CN102336910B (zh) * | 2010-07-14 | 2015-04-08 | 株式会社Lg化学 | 可低温固化的聚酰亚胺树脂及其制备方法 |
KR20130035779A (ko) * | 2011-09-30 | 2013-04-09 | 코오롱인더스트리 주식회사 | 포지티브형 감광성 수지 조성물,이로부터 형성된 절연막 및 유기발광소자 |
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- 2013-01-11 TW TW102101117A patent/TWI473836B/zh active
- 2013-01-11 US US14/349,351 patent/US20140296408A1/en not_active Abandoned
- 2013-01-11 EP EP13735849.5A patent/EP2804185A4/en not_active Withdrawn
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EP2804185A2 (en) | 2014-11-19 |
WO2013105813A3 (ko) | 2013-09-19 |
KR101362518B1 (ko) | 2014-02-14 |
JP5825651B2 (ja) | 2015-12-02 |
EP2804185A4 (en) | 2015-08-12 |
JP2014532977A (ja) | 2014-12-08 |
CN103843073A (zh) | 2014-06-04 |
TWI473836B (zh) | 2015-02-21 |
US20140296408A1 (en) | 2014-10-02 |
KR20130083855A (ko) | 2013-07-23 |
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