CN109988312B - Polyamide acid ester, preparation method, negative polyimide composition and application - Google Patents
Polyamide acid ester, preparation method, negative polyimide composition and application Download PDFInfo
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- CN109988312B CN109988312B CN201910280080.3A CN201910280080A CN109988312B CN 109988312 B CN109988312 B CN 109988312B CN 201910280080 A CN201910280080 A CN 201910280080A CN 109988312 B CN109988312 B CN 109988312B
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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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/123—Unsaturated polyimide precursors the unsaturated 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a polyamic acid ester, a preparation method, a negative polyimide composition and application, wherein the structure of the polyamic acid ester is shown as a formula I; compared with polyamic acid with unmodified side chains, the polyamic acid ester provided by the invention can be directly cured at 200 ℃ or below in a negative polyimide composition, has the dielectric constant of less than 3, even less than 2, shortens the processing time, reduces the power consumption, can meet the requirements of the semiconductor industry better, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of display, and relates to a polyamic acid ester, a preparation method, a negative polyimide composition and application.
Background
In the conventional polyimide film, as the relative dielectric constant (i.e., 3.5 or more) of the interlayer film to be formed becomes higher, the increase of the delay time and the increase of power consumption become serious problems, and since many substrate materials cannot withstand a high temperature of 300 degrees or more, most of the polyimides have an imidization temperature of 300 degrees or more.
CN105612441A discloses a polyimide composition, which is a polyimide composition used in an alignment film for an anisotropic pigment film, the polyimide composition comprising a polyimide and a solvent, the polyimide being represented by the following structure.
X represents a 4-valent aliphatic hydrocarbon group having 5 or more carbon atoms; r 1 Indicating toolA 2-valent organic group having an aromatic ring; n represents an integer of 1 or more, and when n is 2 or more, a plurality of R's are present in 1 molecule of the structure represented by the above 1 And X, each of which is the same or different. The polyimide having a specific structure of the present invention has excellent solubility in a solvent, does not require imidization at a high temperature after coating, can remove only the solvent of a coating film at a low temperature, and can form an alignment film on a material such as a color filter, but cannot solve the problem of dielectric properties.
CN103443697A discloses a liquid crystal aligning agent which can reduce fine irregularities on the surface of a liquid crystal alignment film, improve the liquid crystal alignment property, improve the electrical characteristics, and improve the reliability. A polyamic acid comprising a polyamic acid ester having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), the polyamic acid ester having a 2-valent organic group (Y) 1 ) And the 2-valent organic group (Y) of the polyamic acid 2 ) More than 60 mol% of the compounds have the same structure.
X 1 And X 2 Each independently is a 4-valent organic radical, Y 1 And Y 2 Each independently being a 2-valent organic radical, A 1 、A 2 Each independently represents a hydrogen atom or an alkyl, alkenyl or alkynyl group having 1 to 10 carbon atoms which may have a substituent, R 1 Is methyl. This method cannot lower the imidization temperature.
CN102893209A discloses a liquid crystal aligning agent, which contains the following components (a) and (B). Component (A): a polyamic acid ester having a repeating unit represented by the following formula and satisfying the following conditions
In the formula X 1 Is a 4-valent organic radical, Y 1 Is a 2-valent organic radical, R 1 Is an alkyl group having 1 to 5 carbon atoms, A 1 And A 2 Each independently represents a hydrogen atom, or an alkyl group or alkenyl group having 1 to 20 carbon atoms which may have a substituent. This method can only solve the problem of orientation and cannot lower the imidization temperature.
Therefore, it is industrially very important to develop a polyimide composition having a low dielectric constant and capable of completing imidization at 200 ℃ or less.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a polyamic acid ester, a preparation method, a negative polyimide composition and application, so that the composition can form polyimide through low-temperature heat treatment at 200 ℃ or below and the dielectric constant can reach the effect of below 3.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyamic acid ester having a structure represented by formula I:
wherein R is 1 Is a tetravalent organic radical, R 2 Is a divalent organic radical, R 3 Is C 1 ～C 20 Alkyl of (C) 3 ～C 20 A combination of any one or a combination of at least two of the cycloalkyl group or the monovalent organic group having an acrylate structure and an aminopropyl isobutyl silsesquioxane group; n is 150 to 300, and may be, for example, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, or the like.
According to the polyamic acid ester provided by the invention, ester bonds or amido bonds are introduced on the side chain of the polymer repeating unit, so that the curing temperature and the dielectric constant of polyimide can be obviously reduced, compared with polyamic acid of which the side chain is not modified, the polyamic acid ester can be directly cured at 200 ℃ or below, the dielectric constant can reach less than 3 and even less than 2, the processing time is shortened, the power consumption is reduced, and the polyamic acid ester can better meet the requirements of the semiconductor industry.
Said C of the invention 1 ～C 20 The alkyl group of (A) may be C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 、C 20 More specifically, the alkyl group of (1) may be a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-decyl group, an octadecyl group or an eicosyl group, etc.
Preferably, said R is 1 Is composed of
Wherein the dotted line represents the position of the attachment of the group in formula I, X is any one of an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a perarylpolysiloxane, an unsubstituted or fluorine-substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkyl group, R is an alkyl group 4 And R 5 Independently selected from unsubstituted or fluoro substituted aliphatic hydrocarbon groups.
The aliphatic hydrocarbon group of the present invention may be C 1 ～C 20 More specifically, methyl, ethyl, dodecyl, octadecyl or eicosyl, etc.
Preferably, said R is 2 Is composed of
Wherein the dotted line represents the access position of the group in formula I, and Y is any one of an oxygen atom, a sulfur atom, an alkyl group, a sulfonyl group, a carbonyl group, a wholly aromatic polysiloxane, an unsubstituted or fluorine-substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic diether group.
Preferably, said R is 3 Is a combination of a monovalent organic group containing an acrylate structure and an aminopropyl isobutyl silsesquioxane group.
Preferably, said R is 1 Is composed of
Wherein the dotted line indicates the position of the attachment of the group in formula I.
Preferably, said R is 2 Is composed of
Wherein the dotted line indicates the position of the attachment of the group in formula I.
Preferably, said R is 3 Is a combination of 2-hydroxy-n-propyl methacrylate and aminopropyl isobutyl silsesquioxane. Compared with the single use of aminopropyl isobutyl silsesquioxane, the polyamic acid ester loses the photosensitive property, and the combination of the aminopropyl isobutyl silsesquioxane and the polyamic acid ester can ensure the lowest dielectric constant under the condition of photosensitivity; compared with the modification by singly using alkyl, cycloalkyl or univalent organic groups containing acrylate structures, the dielectric property of the modified acrylic acid is better.
In the present invention, R in the structure of the polyamic acid ester 3 It is preferred to use a combination of 2-hydroxy n-propyl methacrylate and aminopropyl isobutyl silsesquioxane groups, i.e. the carboxyl side chain of the polyamic acid ester comprises both an ester bond with glycidyl methacrylate and an amide bond with aminopropyl isobutyl silsesquioxane (aminopropyl isobutyl POSS) groups. Wherein the aminopropylisobutyl POSS has the following structure:
as can be seen from the structure, the structure has voids, which can form nano-scale voids, and since the dielectric constant of air is 1 and air can be contained in the voids, the dielectric constant can be significantly reduced without affecting the optical properties of the system.
Preferably, in 1mol of the structure shown in the formula I, the molar ratio of 2-hydroxy-n-propyl methacrylate to aminopropyl isobutyl silsesquioxane is (5-10): 1; preferably (7-9) 1.
The meaning of the above molar ratio is as follows: for example, assuming that the number of repeating units is 6, i.e., n in the structure shown in formula I is 6, if the molar ratio is 5.
In the preparation process, the reactivity of the amino group and the carboxyl group in the aminopropyl isobutyl POSS is stronger than that of glycidyl methacrylate and the carboxyl group, so the molar ratio of the amino group and the carboxyl group in the polymer can be finally controlled by controlling the feeding ratio of the amino group and the carboxyl group, and the dielectric property of the final system can be optimized.
In the present invention, it is preferable to control the molar ratio of 2-hydroxy-n-propyl methacrylate group to aminopropyl isobutyl silsesquioxane group to be in the above range, particularly in the range of (7 to 9): 1, so that the dielectric constant of the system can be 1.9 to 2.4 or less at a frequency of 10 to 7 and the dielectric properties are excellent.
In a second aspect, the present invention provides a method for preparing polyamic acid ester according to the first aspect, comprising the steps of: mixing the compound a and the compound b, reacting in the first stage, adding R 3 A is continuously carried out the second stage reaction to obtain the polyamic acid ester, and the structure of the compound a is
The structure of the compound b is H 2 N-R 2 NH 2 A is-OH or-NH 2 Wherein R is 1 、R 2 And R 3 Same as the range defined in the first aspect, i.e. R 1 Is a tetravalent organic radical, R 2 Is a divalent organic radical, R 3 Is C 1 ～C 20 Alkyl of (C) 3 ～C 20 Or a combination of at least two of the above monovalent organic groups having an acrylate structure and an aminopropyl isobutyl silsesquioxane group.
Preferably, compound a, compound b and R 3 The molar ratio of A is 1 (0.8-1) to 2-2.2, and for example, 1And the like.
Preferably, the temperature of the first stage reaction is 20-40 ℃, for example, 20 ℃, 22 ℃, 25 ℃, 26 ℃, 27 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 35 ℃, 38 ℃ or 40 ℃.
Preferably, the time of the first stage reaction is 1 to 5 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc.
Preferably, the second stage reaction is carried out in the presence of a catalyst and a polymerization inhibitor.
Preferably, the catalyst is benzyldimethylamine.
Preferably, the polymerization inhibitor is hydroquinone and/or hydroquinone.
In the present invention, a person skilled in the art can add catalyst, polymerization inhibitor and the like in an amount suitable for the reaction process according to actual conditions.
Preferably, the temperature of the second stage reaction is 30-60 ℃, for example, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 50 ℃, 52 ℃, 53 ℃, 55 ℃, 57 ℃, 59 ℃ or 60 ℃.
The time of the second stage reaction is preferably 10 to 24 hours, and may be, for example, 10 hours, 11 hours, 12 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or the like.
In a third aspect, the present invention provides a negative polyimide composition comprising the following components in parts by weight: 20-40 parts of polyamic acid ester, 10-20 parts of photoinitiator, 10-20 parts of photocrosslinking agent, 1-5 parts of curing accelerator and 35-60 parts of solvent.
The negative polyimide composition provided by the invention can be imidized at a temperature of 200 ℃ or below and has a dielectric constant of less than 3 by using the polyamic acid ester with a specific structure and the curing accelerator, and has important value for industrial application.
The polyamic acid ester of the present invention may be 20 to 40 parts by weight, for example, 20 parts, 22 parts, 25 parts, 26 parts, 27 parts, 29 parts, 30 parts, 31 parts, 32 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, or the like.
The photoinitiator of the invention is 10 to 20 parts by weight, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, etc.
Preferably, the photoinitiator comprises any one or a combination of at least two of oxime ester compounds, benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin or benzil dimethyl ketal, preferably oxime ester compounds and benzophenone.
The alkyl group in the alkylanthraquinone of the present invention may be a straight-chain alkyl group or a branched-chain alkyl group, etc., which are well known to those skilled in the art.
The oxime ester compound of the invention is
The photocrosslinking agent of the present invention may be present in an amount of 10 to 20 parts by weight, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts.
Preferably, the photocrosslinking agent comprises any one of or a combination of at least two of triethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1, 3-acryloyloxy-2-hydroxypropane, 1, 3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N-dimethylacrylamide, N-methylolacrylamide; preferably tetraethylene glycol dimethacrylate.
The solvent of the present invention is 35 to 60 parts by weight, and may be, for example, 35 parts, 37 parts, 38 parts, 40 parts, 42 parts, 43 parts, 45 parts, 46 parts, 48 parts, 50 parts, 51 parts, 53 parts, 55 parts, 57 parts, 59 parts, 60 parts, or the like.
Preferably, the solvent includes any one of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, or γ -butyrolactone, or a combination of at least two thereof.
The curing accelerator of the present invention may be used in an amount of 1 to 5 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, or 5 parts.
Preferably, the curing accelerator includes any one of or a combination of at least two of a substituted or unsubstituted nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, and an aromatic compound containing nitrogen, a carbonyl group, or at least two hydroxyl groups outside the ring.
In the present invention, the curing accelerator has an effect of accelerating the reduction of the imidization temperature, and can accelerate imidization of the composition at a relatively low temperature, for example, 200 ℃.
Preferably, the nitrogen-containing heterocyclic compound has a pKa value in water of 0 to 8, and may be, for example, 0, 1,2, 3,4, 5,6, 7, 8, or the like.
Preferably, the nitrogen-containing heterocyclic compound includes any one of imidazole, pyrazole, triazole, tetrazole, benzimidazole, naphthoimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, bipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, 2, 3-naphthyridine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, benzoisoquinoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, pyrimidine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, pyrrolidinone, isoindoledione, pyrrolidinedione, benzisoquinolinedione, triethylenediamine, or hexamethylenetetramine. N-oxides of these nitrogen-containing heterocyclic compounds are also possible.
<xnotran> , , , , , , α - , β - , γ - , γ - - β - , , β - , γ - , , β - , γ - , δ - , , , , , α - , , α - , , , , , , , -3- , -3- , ε - , ω - , β - , β - , α - - β - , ε - - δ - , α - - ε - , , , S- , S- -S- , , , , , , , α, β - , , , , , , δ - , , , , , , , α - , β - , γ - , </xnotran> Alpha-aminoadipic acid, citrulline, lanthionine, cystathionine, phenylalanine, alpha-methylphenylalanine, o-chlorophenylalanine, m-chlorophenylalanine, p-chlorophenylalanine, o-fluorophenylalanine, m-fluorophenylalanine, p-fluorophenylalanine, beta- (2-pyridyl) alanine, tyrosine, thyroxine, dichlorotyrosine, dibromotyrosine, diiodotyrosine, 3, 4-dihydroxyphenylalanine, alpha-methyl-3, 4-dihydroxyphenylalanine, phenylglycine, tryptophan, phaseolin, histidine, 1-methylhistidine, 2-mercaptohistidine, proline, hydroxyproline, anthranilic acid, p-aminobenzoic acid, 2-mercaptohistidine, proline, hydroxyproline, or anthranilic acid. It may also be a compound containing a secondary amino group or a substituted amino group.
<xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,4,4' - ,1,6- ,2,6- , (4- ) , (4- ) , (4- ) -1- ,1,2- (4- ) ,1,1- (4- ) -1- ,2- (4- ) -2- (3- ) , (4- ) ,2,2- (4- -3- ) ,1,1- ( ) ,1,1- (4- ) ,1,1- (4- ) ,1,1- (4- ) , -2,3- (4- ) -2- , </xnotran> <xnotran> 2,2- (4- ) , α, α' - (4- ) , (4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ; </xnotran> 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-t-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5, 6-tetrafluororesorcinol, 2,4,5, 6-tetrabromorecinol or catechol.
In the present invention, the amount of the curing accelerator added is preferably 0.2 to 4 times per mole equivalent of the polyamic acid ester repeating unit.
Preferably, the negative polyimide composition further comprises 0.2 to 2 parts of a tackifier, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts and the like.
Preferably, the adhesion promoter comprises any one or a combination of at least two of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, vinyltriethoxysilane, N- (hydroxymethyl) -N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropoxy-5-hydroxyflavone, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, 2-hydroxy-4- (3-methyldiethoxysilylpropoxy) diphenylketone, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane, 3- (N-acetyl-4-hydroxypropoxy) propyltriethoxysilane, or hydroxymethyltriethoxysilane; bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane is preferred.
Preferably, the negative polyimide composition further comprises 0.4-3 parts of a leveling agent, such as 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 1.9 parts, 2 parts, 2.3 parts, 2.5 parts, 2.7 parts, 2.8 parts, 3 parts and the like.
In the invention, the skilled person can select the commonly used leveling agent to add, preferably using acrylic ester as the leveling agent, the number average molecular weight is controlled between 6000-20000, the molecular weight distribution is relatively narrow, the glass transition temperature is controlled below-20 ℃, and the surface tension is controlled below 25-26 mN/m.
In a fourth aspect, the present invention provides a negative polyimide composition according to the third aspect for use in an electronic display device.
Compared with the prior art, the invention has the following beneficial effects:
according to the polyamic acid ester provided by the invention, ester bonds or amido bonds are introduced into the side chain of the polymer repeating unit, so that the curing temperature and the dielectric constant of polyimide can be obviously reduced, compared with polyamic acid with unmodified side chain, the polyamic acid ester can be directly cured at 200 ℃ or below in a negative polyimide composition, the dielectric constant can reach 3 or below, even 2 or below, the processing time is shortened, the power consumption is reduced, the polyamic acid ester can meet the requirements of the semiconductor industry, and the polyamic acid ester has a wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of a polyamic acid ester provided in example 1 of the present invention.
FIG. 2 is a GPC results chart of the polyamic acid ester provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a polyamic acid ester
Wherein R is 3 Is a combination of 2-hydroxy-n-propyl methacrylate and aminopropyl isobutyl silsesquioxane in a ratio of 9.
While stirring, 4' -diaminodiphenyl ether (0.29 mol) was added to pyromellitic anhydride (0.3 mol), stirring was continued for 2 hours at 25 ℃ and then a small amount of 2-hydroxyethyl methacrylate was added to the reaction mixture to bind the terminal anhydride groups still present. After stirring at 30 ℃ for 2 hours, 0.54mol of glycidyl methacrylate and 0.06mol of aminopropylisobutylsilsesquioxane were added to the reaction mixture together with appropriate amounts of benzyldimethylamine and hydroquinone. Subsequently, the solution was heated to a temperature of 60 ℃, stirred for 23 hours, and then added dropwise to ethanol while vigorously stirring. The precipitate formed is withdrawn and dried in vacuo at room temperature to give the polyamic acid ester with an n value of 178.
FIG. 1 shows the infrared results of polyamic acid esters, and it is clear from FIG. 1 that the reaction proceeds smoothly with the attachment of a siloxane-based POSS group.
FIG. 2 shows the GPC results, and it is understood that the weight average molecular weight is 75367.
Example 2
This example provides a polyamic acid ester
Wherein R is 3 Is a combination of 2-hydroxy-n-propyl methacrylate and aminopropyl isobutyl silsesquioxane in a ratio of 5.
While stirring, 4' -diaminodiphenyl ether (0.6 mol) was added to pyromellitic anhydride (0.6 mol), stirring was continued for 2 hours at 25 ℃ and 2-hydroxyethyl methacrylate was then added to the reaction mixture to bind the terminal anhydride groups still present. After stirring at room temperature for 2 hours, 1mol of glycidyl methacrylate and 0.2mol of aminopropylisobutylsilsesquioxane were added to the reaction mixture together with appropriate amounts of benzyldimethylamine and hydroquinone. Subsequently, the solution was heated to a temperature of 60 ℃ and stirred for 23 hours, and then added dropwise to ethanol while vigorously stirring. The precipitate formed was withdrawn and dried in vacuo at room temperature to give a polyamic acid ester having an n value of 120 and a weight average molecular weight of 50788.
Example 3
This example provides a polyamic acid ester
Wherein R is 3 Is a combination of 2-hydroxy-n-propyl methacrylate and aminopropyl isobutyl silsesquioxane groups in a ratio of 9.
While stirring, 4 '-diaminodiphenyl ether (0.29 mol) was added to 4,4' -oxydiphthalic anhydride (0.3 mol), stirring was continued for 2 hours at 30 ℃ and then a small amount of 2-hydroxyethyl methacrylate was added to the reaction mixture to bind the terminal anhydride groups still present. After stirring at 30 ℃ for 2 hours, 0.54mol of glycidyl methacrylate and 0.06mol of aminopropylisobutylsilsesquioxane were added to the reaction mixture together with appropriate amounts of benzyldimethylamine and hydroquinone. Subsequently, the solution was heated to a temperature of 60 ℃ and stirred for 23 hours, and then added dropwise to ethanol while vigorously stirring. The precipitate formed was withdrawn and dried in vacuo at room temperature to give a polyamic acid ester having an n value of 170 and a weight average molecular weight of 71983.
Example 4
This example provides a polyamic acid ester
Wherein R is 3 Is a combination of 2-hydroxy-n-propyl methacrylate and aminopropyl isobutyl silsesquioxane in a ratio of 7.
While stirring, the mixture is stirred
(0.3 mol) 4,4' -diaminodiphenyl ether (0.29 mol) was added, stirring was continued at 30 ℃ for 2 hours and then a small amount of 2-hydroxyethyl methacrylate was added to the reaction mixture in order to bind the terminal anhydride groups still present. After stirring for 2 hours at 30 ℃ 0.525mol of glycidyl methacrylate and 0.075mol of aminopropylisobutylsilsesquioxane and the appropriate amounts of benzyldimethylamine and hydroquinone are added to the reaction mixture. Subsequently, the solution was heated to a temperature of 60 ℃ and stirred for 23 hours, and then added dropwise to ethanol while vigorously stirring. The precipitate formed was withdrawn and dried in vacuo at room temperature to give a polyamic acid ester having an n value of 180 and a weight average molecular weight of 76217.
Comparative example 1
This comparative example differs from example 1 only in that R 3 Is 2-hydroxy-methacrylateN-propyl ester group, namely all the materials fed in the reaction process are glycidyl methacrylate.
Comparative example 2
This comparative example differs from example 1 only in that R 3 Is aminopropyl isobutyl silsesquioxane, namely all the materials fed in the reaction process are aminopropyl isobutyl silsesquioxane.
Comparative example 3
This comparative example differs from example 1 only in that R 3 Is hydrogen, i.e., the esterification reaction of the second stage is not carried out during the reaction.
Example 7
The embodiment provides a negative polyimide composition, which comprises the following components in parts by weight:
30 parts of polyamic acid ester, 16 parts of oxime ester compound, 15 parts of tetraethylene glycol dimethacrylate, 2 parts of quinoline, 1 part of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 1 part of leveling agent and 40 parts of N-methyl-2-pyrrolidone, which are provided in example 1.
Example 8
The embodiment provides a negative polyimide composition, which comprises the following components in parts by weight:
35 parts of polyamic acid ester, 20 parts of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone, 20 parts of diethylene glycol dimethacrylate, 5 parts of gamma-aminobutyric acid, 2 parts of vinyltriethoxysilane, 3 parts of a leveling agent and 60 parts of dimethyl sulfoxide, wherein the parts are provided in example 2.
Example 9
The embodiment provides a negative polyimide composition, which comprises the following components in parts by weight:
example 3 provides 40 parts of polyamic acid ester, 10 parts of N, N '-tetramethyl-4, 4' -diaminobenzophenone, 10 parts of trimethylolpropane dimethacrylate, 1 part of benzodioxane, 0.2 part of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane, 0.4 part of leveling agent, and 40 parts of tetramethylurea.
Example 10
The embodiment provides a negative polyimide composition, which comprises the following components in parts by weight:
example 4 provides polyamide acid ester 26 parts, benzophenone 13 parts, 4-vinylpyridine 14 parts, glutamic acid 3 parts, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane 0.7 parts, leveling agent 1.2 parts, hexamethylphosphoric triamide 35 parts.
Comparative example 4
The comparative example provides a negative polyimide composition comprising the following components in parts by weight:
30 parts of polyamide acid ester, 16 parts of oxime ester compound, 15 parts of tetraethylene glycol dimethacrylate, 2 parts of quinoline, 1 part of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 1 part of leveling agent and 40 parts of N-methyl-2-pyrrolidone, wherein the polyamide acid ester is prepared by the following steps.
Comparative example 5
The comparative example provides a negative polyimide composition comprising the following components in parts by weight:
30 parts of polyamide acid ester, 16 parts of oxime ester compound, 15 parts of tetraethylene glycol dimethacrylate, 2 parts of quinoline, 1 part of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 1 part of leveling agent and 40 parts of N-methyl-2-pyrrolidone, wherein the polyamide acid ester is prepared by the following steps.
Comparative example 6
The comparative example provides a negative polyimide composition comprising the following components in parts by weight:
30 parts of polyamic acid ester, 16 parts of oxime ester compound, 15 parts of tetraethylene glycol dimethacrylate, 2 parts of quinoline, 1 part of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 1 part of leveling agent and 40 parts of N-methyl-2-pyrrolidone, which are provided by the comparative example 3.
The negative polyimide compositions provided in examples 7 to 10 and comparative examples 4 to 6 were subjected to the curing temperature test for imidization (by infrared test) and the dielectric constant (impedance meter) test, and the specific results of the tests are shown in the following table 1:
TABLE 1
| Sample (I) | Imidization ratio (%) | Dielectric constant |
| Example 7 | 98.6 | 2.2 |
| Example 8 | 98.4 | 2.4 |
| Example 9 | 98.3 | 2.1 |
| Example 10 | 98.1 | 2.3 |
| Comparative example 4 | 98.7 | 3.3 |
| Comparative example 5 | 99.1 | 1.9 |
| Comparative example 6 | 98.2 | 3.7 |
As is clear from the results in Table 1, if R is 3 Without aminopropyl isobutyl sesquiIf siloxane is modified properly, the negative polyimide composition has poor dielectric properties and a dielectric constant of more than 3; when R is 3 After the amino propyl isobutyl silsesquioxane is modified in the groups, the dielectric property of the modified amino propyl isobutyl silsesquioxane is greatly improved, and the dielectric constant can generally reach about 2.
In addition, the proper modification of the using amount of aminopropyl isobutyl silsesquioxane is ensured, and infrared spectroscopic analysis and morphology characterization show that the viscosity is rapidly increased along with the increase of the content of POSS, side groups are increased and intertwined with each other, so that cavities are enlarged, the moisture absorption rate is increased, and the dielectric property is reduced; the amount is therefore generally controlled to be 1: (7-9), the dielectric properties can be optimized.
The applicant states that the present invention is illustrated by the above examples of the polyamic acid ester, the preparation method, and the negative polyimide composition and the application of the present invention, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must be implemented depending on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (31)
1. A polyamic acid ester, wherein the polyamic acid ester has a structure according to formula I:
wherein R is 1 Is composed of
Wherein the dotted line represents the position of the group attachment in formula I, X is any one of an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an unsubstituted or fluorine-substituted aliphatic hydrocarbon group or an unsubstituted or fluorine-substituted aromatic hydrocarbon group, and R is 4 And R 5 Independently selected from unsubstituted or fluoro substituted aliphatic hydrocarbyl groups;
R 2 is composed of
Wherein the dotted line represents the access position of the group in formula I, and Y is any one of an oxygen atom, a sulfur atom, an alkyl group, a sulfonyl group, a carbonyl group, an unsubstituted or fluorine-substituted aliphatic hydrocarbon group, an unsubstituted or fluorine-substituted aromatic hydrocarbon group or an aromatic diether group;
R 3 is a combination of a monovalent organic group containing an acrylate structure and aminopropyl isobutyl silsesquioxane;
the value of n is 150-300.
2. Polyamic acid ester according to claim 1, wherein R is 1 Is composed of
Wherein the dotted line indicates the position of the attachment of the group in formula I.
3. Polyamic acid ester according to claim 1, wherein R is 2 Is composed of
Wherein the dotted line indicates the position of the attachment of the group in formula I.
4. Polyamic acid ester according to claim 1, wherein R is 3 Is a combination of 2-hydroxy-n-propyl methacrylate and aminopropyl isobutyl silsesquioxane.
5. The polyamic acid ester according to claim 1, wherein the molar ratio of 2-hydroxy-n-propyl methacrylate group to aminopropyl isobutyl silsesquioxane group in 1mol of the structure represented by formula I is (5-10): 1.
6. The polyamic acid ester according to claim 5, wherein the molar ratio of 2-hydroxy-n-propyl methacrylate to aminopropyl isobutyl silsesquioxane in 1mol of the structure of formula I is (7-9): 1.
7. Process for the preparation of polyamic acid esters according to any one of claims 1 to 6, characterized in that it comprises the following steps: mixing the compound a and the compound b, reacting in the first stage, adding R 3 A is continuously carried out the second stage reaction to obtain the polyamic acid ester, and the structure of the compound a is
The structure of the compound b is H 2 N-R 2 -NH 2 A is-OH or-NH 2 Wherein R is 1 、R 2 And R 3 The same as defined in claim 1. />
8. The method according to claim 7, wherein the compound a, the compound b and R are 3 The molar ratio of A is 1 (0.8-1) to 2-2.2.
9. The method of claim 7, wherein the temperature of the first stage reaction is 20 to 40 ℃.
10. The method of claim 7, wherein the first stage reaction time is 1 to 5 hours.
11. The production method according to claim 7, wherein the second-stage reaction is carried out in the presence of a catalyst and a polymerization inhibitor.
12. The method according to claim 7, wherein the catalyst is benzyldimethylamine.
13. The process according to claim 7, wherein the polymerization inhibitor is hydroquinone and/or hydroquinone.
14. The method according to claim 7, wherein the temperature of the second-stage reaction is 30 to 60 ℃.
15. The method according to claim 7, wherein the reaction time of the second stage is 10 to 24 hours.
16. A negative polyimide composition is characterized by comprising the following components in parts by weight: 20 to 40 parts of polyamide acid ester as described in any one of claims 1 to 6, 10 to 20 parts of photoinitiator, 10 to 20 parts of photocrosslinking agent, 1 to 5 parts of curing accelerator, and 35 to 60 parts of solvent.
17. The negative polyimide composition of claim 16, wherein the photoinitiator comprises any one or a combination of at least two of an oxime ester compound, benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin, or benzoin dimethyl ketal.
18. The negative polyimide composition according to claim 17, wherein the photoinitiator is an oxime ester compound and a benzophenone.
19. The negative polyimide composition of claim 16, wherein the photocrosslinking agent comprises any one or a combination of at least two of tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1, 3-acryloyloxy-2-hydroxypropane, 1, 3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N-dimethylacrylamide, N-methylolacrylamide.
20. The negative polyimide composition of claim 19, wherein the photocrosslinker is tetraethylene glycol dimethacrylate.
21. The negative polyimide composition according to claim 16, wherein the solvent comprises any one of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, or γ -butyrolactone, or a combination of at least two thereof.
22. The negative polyimide composition according to claim 16, wherein the curing accelerator comprises any one of or a combination of at least two of a substituted or unsubstituted nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, and an aromatic compound containing nitrogen, a carbonyl group, or at least two hydroxyl groups outside the ring.
23. The negative polyimide composition according to claim 22, wherein the nitrogen-containing heterocyclic compound has a pKa value in water of 0 to 8.
24. The negative polyimide composition according to claim 22, wherein the nitrogen-containing heterocyclic compound comprises any one of imidazole, pyrazole, triazole, tetrazole, benzimidazole, naphthoimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, bipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, 2, 3-naphthyridine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, phenylquinoline, benzisoquinoline, benzoquinoline, phthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, pyrimidine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, pyrrolidinedione, isoindoledione, pyrrolidinedione, benzisoquinolinedione, triethylenediamine, or hexamethylenetetramine.
25. The negative polyimide composition according to claim 22, wherein the amino acid-based compound comprises glycine, sarcosine, dimethylglycine, betaine, alanine, α -aminobutyric acid, β -aminobutyric acid, γ -amino- β -oxobutyric acid, valine, β -aminoisovaleric acid, γ -aminoisoprene, norvaline, β -aminovaleric acid, γ -aminovaleric acid, δ -aminovaleric acid, leucine, isoleucine, norleucine, serine, α -methylserine, isoserine, α -methylisoterine, cycloserine, homoserine, threonine, o-methylthreonine, isothreonine, o-methylisothreonine, trans-3-cyclohexanecarboxylic acid, cis-3-aminocyclohexanecarboxylic acid, ε -aminocaproic acid, ω -aminododecanoic acid, β -hydroxyvaline, β -hydroxyisoleucine, α -hydroxy- β -aminoisovaleric acid, ε -diazo- δ -oxoleucine, α -amino- ε -hydroxyaminocaproic acid, cystine, S-methylcysteine, S-homocysteine, cysteine oxide, beta-diaminopropionic acid, ornithine, lysine, arginine, canavanic acid, delta-hydroxylysine, aspartic acid, asparagine, isoasparagine, glutamic acid, glutamine, isoglutamine, alpha-methylglutamic acid, beta-hydroxyglutamic acid, gamma-hydroxyglutamic acid, alpha-aminoadipic acid, citrulline, lanthionine, cystathionine, phenylalanine, alpha-methylphenylalanine, o-chlorophenylalanine, m-chlorophenylalanine, p-chlorophenylalanine, o-fluorophenylalanine, m-fluorophenylalanine, p-fluorophenylalanine, beta- (2-pyridyl) alanine, tyrosine, thyroxine, dichlorotyrosine, dibromotyrosine, diiodotyrosine, 3, 4-dihydroxyphenylalanine, alpha-methyl-3, 4-dihydroxyphenylalanine, phenylglycine, tryptophan, abrine, histidine, 1-methylhistidine, 2-mercaptohistidine, proline, hydroxyproline, anthranilic acid, p-aminobenzoic acid, 2-mercaptohistidine, proline, hydroxyproline or anthranilic acid.
26. <xnotran> 22 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,4,4' - ,1,6- ,2,6- , (4- ) , (4- ) , (4- ) -1- ,1,2- (4- ) ,1,1- (4- ) -1- ,2- (4- ) -2- (3- ) , (4- ) ,2,2- (4- -3- ) ,1,1- ( ) ,1,1- (4- ) ,1,1- (4- ) ,1,1- (4- ) , </xnotran> <xnotran> -2,3- (4- ) -2- ,2,2- (4- ) , α, α' - (4- ) , (4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) ; </xnotran> 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-t-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5, 6-tetrafluororesorcinol, 2,4,5, 6-tetrabromorecinol or catechol.
27. The negative polyimide composition according to claim 16, further comprising 0.2 to 2 parts of a tackifier.
28. The negative polyimide composition of claim 27, wherein the adhesion promoter comprises any one of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, vinyltriethoxysilane, N- (hydroxymethyl) -N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropoxy-5-hydroxyflavone, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, 2-hydroxy-4- (3 methyldiethoxysilylpropoxy) diphenylketone, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane, 3- (N-acetyl-4-hydroxypropoxy) propyltriethoxysilane, or hydroxymethyltriethoxysilane, or a combination of at least two thereof.
29. The negative polyimide composition of claim 28, the adhesion promoter being bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane.
30. The negative polyimide composition according to claim 16, further comprising 0.4 to 3 parts of a leveling agent.
31. Use of the negative polyimide composition of any one of claims 16-30 in an electronic display device.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004341165A (en) * | 2003-05-15 | 2004-12-02 | Chisso Corp | Varnish for forming liquid crystal alignment layer, and liquid crystal display element |
| CN101003768A (en) * | 2005-12-28 | 2007-07-25 | 高爽工业公司 | Foamable alcoholic composition |
| CN102449031A (en) * | 2009-04-02 | 2012-05-09 | 日产化学工业株式会社 | Polyimide precursor composition containing polyamic alkyl ester |
| US9006371B1 (en) * | 2010-09-28 | 2015-04-14 | United States Of America As Represented By The Secretary Of The Navy | Synthesis of oligomeric silsesquioxane monomers for high performance polymers |
| CN105837819A (en) * | 2016-05-25 | 2016-08-10 | 常州大学 | Hybrid polyimide containing trifluoromethyl and oligomeric silsesquioxane structures at same time and preparation method thereof |
| CN107922733A (en) * | 2015-08-07 | 2018-04-17 | 东京应化工业株式会社 | Polyimide precursor composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160237311A1 (en) * | 2013-09-26 | 2016-08-18 | Farhad G. Mizori | Low dielectric constant, low dielectric dissipation factor coatings, films and adhesives |
-
2019
- 2019-04-09 CN CN201910280080.3A patent/CN109988312B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004341165A (en) * | 2003-05-15 | 2004-12-02 | Chisso Corp | Varnish for forming liquid crystal alignment layer, and liquid crystal display element |
| CN101003768A (en) * | 2005-12-28 | 2007-07-25 | 高爽工业公司 | Foamable alcoholic composition |
| CN102449031A (en) * | 2009-04-02 | 2012-05-09 | 日产化学工业株式会社 | Polyimide precursor composition containing polyamic alkyl ester |
| US9006371B1 (en) * | 2010-09-28 | 2015-04-14 | United States Of America As Represented By The Secretary Of The Navy | Synthesis of oligomeric silsesquioxane monomers for high performance polymers |
| CN107922733A (en) * | 2015-08-07 | 2018-04-17 | 东京应化工业株式会社 | Polyimide precursor composition |
| CN105837819A (en) * | 2016-05-25 | 2016-08-10 | 常州大学 | Hybrid polyimide containing trifluoromethyl and oligomeric silsesquioxane structures at same time and preparation method thereof |
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