CN109988312A - A kind of poly amic acid ester, preparation method and negative polyimide composition and application - Google Patents
A kind of poly amic acid ester, preparation method and negative polyimide composition and application Download PDFInfo
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- CN109988312A CN109988312A CN201910280080.3A CN201910280080A CN109988312A CN 109988312 A CN109988312 A CN 109988312A CN 201910280080 A CN201910280080 A CN 201910280080A CN 109988312 A CN109988312 A CN 109988312A
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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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- 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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- 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
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of poly amic acid ester, preparation method and negative polyimide composition and application, the structure of the poly amic acid ester is shown in formula I；Poly amic acid ester provided by the present invention, by introducing ester bond or amido bond on the side chain of polymer repeat unit, the solidification temperature and dielectric constant of polyimides, the polyamic acid not being modified compared to side chain can be significantly reduced, in negative polyimide composition, can directly at 200 DEG C and it is following solidified, and dielectric constant can reach 3 hereinafter, even up to 2 or less, shorten process time, power consumption is reduced, is better able to adapt to the requirement of semi-conductor industry, have a extensive future.
Description
Technical field
The invention belongs to field of display technology, it is related to a kind of poly amic acid ester, preparation method and negative polyimide group
Close object and application.
Background technique
Existing polyimide film, with the interlayer film of formation relative dielectric constant (i.e. 3.5 or 3.5 or more) increasingly
Height, the increase of delay time and the increase of power consumption become serious problem, and because many baseplate materials can not bear 300
Degree or more high temperature, and the imidization temperature of most of polyimides is all at 300 degree or more.
CN105612441A discloses a kind of polyimide compositions, is that anisotropy pigmented film is used in alignment films
Polyimide compositions, polyimide compositions include polyimides and solvent, the polyimides is by following representation.
4 valence aliphatic alkyls of X 5 or more carbon atom number of expression；R1Indicate the divalent organic group with aromatic rings；N is indicated
1 or more integer, when n is 2 or more, multiple R present in the structure of the above-mentioned expression of 1 molecule1And X, it is respectively identical or not
Together.The dissolubility of the polyimides of the specific structure of the invention in a solvent is excellent, without carrying out acyl under high temperature after coating
Imidization can only be coated the solvent removal of film at low temperature, can form alignment films on the materials such as colour filter,
But it can not be solved the problems, such as in its dielectric properties.
CN103443697A discloses a kind of aligning agent for liquid crystal, which can be reduced the surface of liquid crystal orientation film
Fine bumps, liquid crystal aligning improves, and electrical characteristics are also improved, and reliability improves.Containing with following formula (1) table
The polyamic acid of the poly amic acid ester of the repetitive unit shown and the repetitive unit indicated with following formula (2), the polyamic acid
Divalent organic group (Y possessed by ester1) and the polyamic acid possessed by divalent organic group (Y2) there are 60 moles of % or more to have
There is identical structure.
X1And X2It is separately 4 valence organic groups, Y1And Y2It is separately divalent organic group, A1、A2It is only respectively
It is on the spot hydrogen atom or alkyl, alkenyl or the alkynyl of the carbon number 1~10 that can have substituent group, R1For methyl.The method without
The temperature of method reduction imidization.
CN102893209A discloses a kind of aligning agent for liquid crystal, contains following (A) ingredient and (B) ingredient.(A) ingredient: tool
There is the repetitive unit of following formula expression and meets the poly amic acid ester of following conditions
X in formula1It is 4 valence organic groups, Y1It is divalent organic group, R1It is the alkyl of carbon number 1~5, A1And A2Separately
For hydrogen atom or alkyl, the alkenyl of the carbon number 1~20 that can have substituent group.The method is merely capable of solving asking for orientation
Topic, can not reduce the temperature of imidization.
Therefore, how to develop with lower dielectric constant and can be in 200 DEG C and the polyamides of imidizate accomplished below
Imines composition has very important industry meaning.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of poly amic acid esters, preparation method and negative
Property polyimide compositions and application, enable composition to form polyimides by 200 DEG C and Low Temperature Heat Treatment below,
And dielectric constant reaches 3 effects below.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the structure of the poly amic acid ester is shown in formula I the present invention provides a kind of poly amic acid ester:
Wherein, R1For quadrivalent organic radical group, R2For bivalent organic group, R3For C1~C20Alkyl, C3~C20Naphthenic base
In the monovalent organic group containing acrylate structural any one or at least two combination and aminopropyl isobutyl group times
The combination of half siloxy group；The value of n is 150~300, for example, can be 150,160,170,180,190,200,210,220,
230,240,250,260,270,280,290 or 300 etc..
Poly amic acid ester provided by the invention, by introducing ester bond or amido bond on the side chain of polymer repeat unit,
The solidification temperature and dielectric constant that polyimides can be significantly reduced can be straight compared to the polyamic acid that side chain is not modified
Connect at 200 DEG C and it is following solidified, and dielectric constant can reach 3 hereinafter, even up to 2 hereinafter, shorten process time,
Power consumption is reduced, is better able to adapt to the requirement of semi-conductor industry.
C of the present invention1~C20Alkyl can be C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、
C15、C16、C17、C18、C19、C20Alkyl, more specifically can be methyl, ethyl, isopropyl, tert-butyl, positive decyl, octadecane
Base or eicosyl etc..
Preferably, the R1ForIn any one, wherein empty
Line indicates the on-position of the group in Formulas I, and X is oxygen atom, sulphur atom, sulfonyl, carbonyl, full aryl polysiloxane, does not take
Generation or fluorine-substituted aliphatic group, aryl radical or alkyl in any one, R4And R5Replace independently selected from unsubstituted or fluorine
Aliphatic group.
Aliphatic group of the present invention can be C1~C20Aliphatic hydrocarbon, be more specifically methyl, ethyl, dodecyl,
Octadecyl or eicosyl etc..
Preferably, the R2ForWherein dotted line indicates the on-position of the group in Formulas I, Y
For oxygen atom, sulphur atom, alkyl, sulfonyl, carbonyl, full aryl polysiloxane, unsubstituted or fluorine-substituted aliphatic group, fragrance
Any one in alkyl or fragrant two ethers.
Preferably, the R3For the monovalent organic group containing acrylate structural and aminopropyl isobutyl group silsesquioxane
The combination of base.
Preferably, the R1ForWherein dotted line indicates the on-position of the group in Formulas I.
Preferably, the R2ForWherein dotted line indicates the on-position of the group in Formulas I.
Preferably, the R3For methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane-based
Combination.Light sensitive characteristic will be lost compared to the aminopropyl isobutyl group silsesquioxane-based poly amic acid ester is used alone, the two is mixed
With can guarantee to possess lowest dielectric constant with light sensitivity；Compared to be used alone alkyl, naphthenic base or
Monovalent organic group containing acrylate structural is modified, and dielectric properties are more excellent.
In the present invention, in the structure of poly amic acid ester, R3It is preferable to use methacrylic acid -2- hydroxyl n-propyl base and ammonia
The combination of propyl isobutyl group silsesquioxane-based, the i.e. carboxylic side-chain of poly amic acid ester had both included and methyl propenoic acid glycidyl
The ester bond that ester is formed, and include the amido bond formed with aminopropyl isobutyl group silsesquioxane (aminopropyl isobutyl group POSS) base.
Wherein, the structure of aminopropyl isobutyl group POSS is as follows:
By its structure it is found that the structure has cavity, nanoscale cavity can be formed, since the dielectric constant of air is
1, air can be contained in cavity, therefore dielectric constant can be significantly reduced in the case where not influencing the optical property of system.
Preferably, in the structure shown in 1mol Formulas I, methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group
The molar ratio of silsesquioxane-based is (5~10): 1；Preferably (7~9): 1.
The meaning of above-mentioned molar ratio is as follows: for example, it is assumed that the number of repetitive unit is 6, i.e., the n value in structure shown in Formulas I
It is 6, it is a containing methacrylic acid -2- hydroxyl n-propyl base in the structure of poly amic acid ester at this time if molar ratio is 5:1
Number is 5, and the number of aminopropyl isobutyl group POSS base is 1.
During the preparation process, since the reactivity of amino and carboxyl in aminopropyl isobutyl group POSS is compared to methyl-prop
The reactivity of olefin(e) acid ethylene oxidic ester and carboxyl is stronger, therefore, can pass through both the feed ratio of both control, final control
Molar ratio in the polymer, so that final system dielectric properties reach best.
In the present invention, it is preferred to control methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane
The molar ratio of base is under aforementioned proportion, especially in (7~9): when in 1 range, can make system under 10 7 power frequencies, be situated between
Electric constant reaches 1.9~2.4 even lower, and dielectric properties are excellent.
Second aspect, a kind of preparation method of poly amic acid ester as described in relation to the first aspect provided by the invention, feature
It is, the preparation method comprises the following steps: compound a is mixed after the first stage reacts with compound b, is added
R3A continues second stage and reacts to obtain poly amic acid ester, and the structure of compound a isThe structure of compound b
For H2N-R2NH2, A is-OH or-NH2, wherein R1、R2And R3It is identical as the range limited in first aspect, i.e. R1It is organic for tetravalence
Group, R2For bivalent organic group, R3For C1~C20Alkyl, C3~C20Naphthenic base or monovalence containing acrylate structural
In organic group any one or at least two combination and aminopropyl isobutyl group silsesquioxane-based combination.
Preferably, compound a, compound b and R3The molar ratio of A is 1:(0.8~1): (2~2.2), such as can be 1:
0.8:2,1:0.9:2.1,1:0.98:2.12 or 1:1:2.2 etc..
Preferably, the temperature of the first stage reaction is 20~40 DEG C, such as can be 20 DEG C, 22 DEG C, 25 DEG C, 26
DEG C, 27 DEG C, 29 DEG C, 30 DEG C, 31 DEG C, 32 DEG C, 35 DEG C, 38 DEG C or 40 DEG C etc..
Preferably, the time of the first stage reaction is 1~5h, such as can be 1h, 2h, 3h, 4h, 5h etc..
Preferably, the second stage reaction carries out in the presence of catalyst and polymerization inhibitor.
Preferably, the catalyst is benzyl dimethylamine.
Preferably, the polymerization inhibitor is hydroquinone and/or quinhydrones.
In the present invention, those skilled in the art can add the catalyst for being suitble to reaction process dosage according to the actual situation
With polymerization inhibitor etc..
Preferably, the temperature of the second stage reaction is 30~60 DEG C, such as can be 30 DEG C, 32 DEG C, 35 DEG C, 38
DEG C, 40 DEG C, 42 DEG C, 45 DEG C, 50 DEG C, 52 DEG C, 53 DEG C, 55 DEG C, 57 DEG C, 59 DEG C or 60 DEG C etc..
Preferably, the time of second stage reaction be 10~for 24 hours, such as can be 10h, 11h, 12h, 15h, 16h,
17h, 18h, 19h, 20h, 21h, 22h, 23h or for 24 hours etc..
The third aspect, the present invention provides a kind of negative polyimide composition, the negative polyimide composition is pressed
Parts by weight meter includes following components: 20~40 parts of poly amic acid ester described in first aspect, and 10~20 parts of photoinitiator, photo-crosslinking
10~20 parts of agent, 1~5 part of curing accelerator, 35~60 parts of solvent.
Negative polyimide composition provided by the invention passes through the poly amic acid ester of specific structure and curing accelerator
It uses, composition can be made to carry out imidizate in 200 DEG C and following temperature while there are 3 dielectric constants below, for
Its industrial application has important value.
The parts by weight of poly amic acid ester of the present invention be 20~40 parts, such as can be 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 or 40 parts etc..
The parts by weight of photoinitiator of the present invention are 10~20 parts, such as can be 10 parts, 11 parts, 12 parts, 13 parts, 14
Part, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts etc..
Preferably, the photoinitiator includes oxime ester compound, benzophenone, N, N'- tetramethyl -4,4'- diamino two
Benzophenone, 2- benzyl-2- dimethylamino-1- (4- morpholinyl phenyl) butanone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2-
It is any in quinoline base -1- acetone, alkyl-anthraquinone, benzoin alkylether, benzoin, alkyl benzoin or benzil dimethyl ketal
It is a kind of or at least two combination, preferably oxime ester compound and benzophenone.
Alkyl in alkyl-anthraquinone of the present invention can be straight chained alkyl or branch well known to those skilled in the art
Alkyl etc..
Oxime ester compound of the present invention is
The parts by weight of photocrosslinking agent of the present invention are 10~20 parts, such as can be 10 parts, 11 parts, 12 parts, 13 parts, 14
Part, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts etc..
Preferably, the photocrosslinking agent include dimethacrylate tetraethylene-glycol ester, diethylene glycol diacrylate,
Triethylene glycol diacrylate, tetraethylene glycol diacrylate, dimethacrylate, triethylene glycol dimethyl propylene
Olefin(e) acid ester, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane trimethacrylate, three
Hydroxymethyl-propane dimethylacrylate, trimethylol-propane trimethacrylate, 1,4 butanediol diacrylate, 1,6-
Hexanediyl ester, 1,4- butanediol dimethylacrylate, 1,6-HD dimethylacrylate, pentaerythrite three
Acrylate, pentaerythritol tetraacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, benzene
Ethylene, divinylbenzene, 4- vinyltoluene, 4-vinylpridine, n-vinyl pyrrolidone, methacrylic acid 2- hydroxyl second
Ester, acrylic acid 2- hydroxy methacrylate, 1,3- acryloxy -2- hydroxy propane, 1,3- methacryloxy -2- hydroxy propane,
Methylene-bisacrylamide, N, any one in N- dimethylacrylamide, N hydroxymethyl acrylamide or at least two
Combination；Preferably dimethacrylate tetraethylene-glycol ester.
The parts by weight of solvent of the present invention be 35~60 parts, such as can be 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 or 60 parts etc..
Preferably, the solvent includes n-methyl-2-pyrrolidone, n,N-dimethylacetamide, N, N- dimethyl formyl
In amine, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide or gamma-butyrolacton any one or at least two group
It closes.
The parts by weight of curing accelerator of the present invention are 1~5 part, such as can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts
Deng.
Preferably, the curing accelerator include substituted or unsubstituted nitrogen-containing heterocycle compound, it is substituted or unsubstituted
In the outer aromatic compound containing nitrogen, carbonyl or at least two hydroxyls of amino acids, ring any one or at least
Two kinds of combination.
In the present invention, curing accelerator has the effect of promoting to reduce imidizate temperature, composition can be promoted to exist
Such as 200 DEG C or less progress imidizates under lower temperature.
Preferably, the pKa value of the nitrogen-containing heterocycle compound in water is 0~8, for example, can be 0,1,2,3,4,5,6,
7 or 8 etc..
Preferably, the nitrogen-containing heterocycle compound includes imidazoles, pyrazoles, triazole, tetrazolium, benzimidazole, naphtho- imidazoles, Yin
Azoles, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinolin, bipyridyl, two quinolyls, pyridazine, pyrimidine,
Pyrazine, 2,3- benzodiazine, quinoxaline, quinazoline, cinnolines, naphthyridines, acridine, phenanthridines, benzene quinoline, benzisoquinoline, benzo quinoline
Quinoline, benzo phthalazines, Benzoquinoxalines, Benzoquinazole, phenanthroline, azophenlyene, carboline, pyrimidine, triazine, tetrazine, pteridine, oxazole,
Benzoxazoles, isoxazole, benzo isoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazoles, thiadiazoles, pyrroles
It is any in alkane diketone, isoindoledione, pyrrolidine-diones, benzene isoquinolin diketone, triethylenediamine or hexa
It is a kind of.It is also possible to the N- oxide of these nitrogen-containing heterocycle compounds.
Preferably, the amino acids include glycine, sarcosine, dimethylglycine, glycine betaine, the third ammonia
Acid, butyrine, beta-aminobutyric acid, γ-aminobutyric acid, gamma-amino-β-ketobutyric acid, valine, beta-amino isovaleric acid,
Gamma-amino isoamyl removes first valine, is beta-amino valeric acid, gamma-amino valeric acid, δ-aminovaleric acid, leucine, isoleucine, just bright
Propylhomoserin, serine, Alpha-Methyl serine, isoerine, Alpha-Methyl isoerine, seromycin, homoserine, threonine, neighbour
Methylthreonine, isothreonine, adjacent methyl isothreonine, trans- -3- cyclohexane-carboxylic acid, cis- -3- cyclohexanecarboxylic acid, ε -
Amine caproic acid, omega-amino dodecanoic acid, beta-hydroxy valine, beta-hydroxy isoleucine, Alpha-hydroxy-beta-amino isovaleric acid, ε-weight
Nitrogen-δ-oxo leucine, alpha-amido-ε-hydroxyl amino caproic acid, cysteine, cystine, S- methyl cysteine, S- methyl half
Cystine-S- oxide, cysteine, homocysteine, homocystine, methionine, penicillamine, taurine, α, β-diamino
Propionic acid, ornithine, lysine, arginine, canaline, canavanine, δ-hydroxylysine, aspartic acid, asparagine, different asparagus fern
Amide, glutamic acid, glutamine, isoglutamine, Alpha-Methyl glutamic acid, beta-hydroxyglutamic acid, γ-Hydroxy GIutaminic Acid, α-ammonia
Base adipic acid, citrulling, lanthionine, cystathionie, phenylalanine, Alpha-Methyl phenylalanine, o- chlorophenylalanine, m- chlorine
Phenylalanine, fenclonine, adjacent fluorophenylalanine, fluorophenylalanine, P-fluoropnenylalanine, β-(2- pyridyl group) third ammonia
Acid, tyrosine, thyroxine, dichloro tyrosine, bromotiren, diiodotyrosine, 3,4- dihydroxyphenylalanine, α-first
Base -3,4- dihydroxyphenylalanine, phenylglycine, tryptophan, abrine, histidine, 1-Methyl histidine, 2- sulfydryl group
Propylhomoserin, proline, hydroxy-proline, ortho-aminobenzoic acid, p-aminobenzoic acid, 2-Thiolhistidine, proline, hydroxyproline
Or any one in ortho-aminobenzoic acid.It is also possible to the compound containing secondary amino group or substituted-amino.
Preferably, the aromatic compound includes benzene, anthraquinone, phenanthrenequione, Fluorenone, pyrroles, indoles, iso-indoles, carbazole, furan
It mutters, coumarone, isobenzofuran, thiophene, benzothiophene, dibenzothiophenes, benzodioxole, benzdioxan, connection
Benzene, acetophenone, propiophenone, butyrophenone, benzophenone, benzoic ether, benzene dicarboxylic acid diester, benzamide, benzonitrile, benzene first
Aldehyde, nitrobenzene, benzene sulfonic acid, aniline, diphenylamines, diphenyl methylamine, triphenylamine, triphenylmenthane, triphenylcarbinol, diphenyl methylene ring
Hexadiene ketone, 4,4' dihydroxy diphenyl, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, bis- (4- hydroxy phenyl) methane, bis- (4- hydroxyls
Base phenyl) diphenyl methane, bis- (4- hydroxy phenyl) -1- naphthyl methanes, bis- (4- hydroxy phenyl) ethane of 1,2-, the bis- (4- of 1,1-
Hydroxy phenyl) -1- diphenylphosphino ethane, 2- (4- hydroxy phenyl) -2- (3- hydroxy phenyl) propane, bis- (4- hydroxy phenyl) phenyl first
Bis- (4- hydroxyl -3- bromophenyl) propane of alkane, 2,2-, bis- (hydroxy phenyl) pentamethylene of 1,1-, bis- (4- hydroxy phenyl) hexamethylenes of 1,1-
Bis- (4- hydroxy phenyl) isobutenes of alkane, 1,1-, bis- (4- hydroxy phenyl) cyclododecanes of 1,1-, bis- (the 4- hydroxy benzenes of trans- -2,3-
Base) -2- butylene, 2,2- bis- (4- hydroxy phenyl) adamantane, α, bis- (4- hydroxy phenyl) toluene of α ' -, bis- (4- hydroxy phenyl) second
Bis- (3- ethyl -4- hydroxy phenyl) propane of nitrile, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 2,2-, the bis- (3- positive third of 2,2-
Base -4- hydroxy phenyl) propane, bis- (3- isopropyl -4- hydroxy phenyl) propane of 2,2-, the bis- (3- sec-butyl -4- hydroxy benzenes of 2,2-
Base) propane, bis- (3- tert-butyl-hydroxy phenyl) propane of 2,2-, 2,2- bis- (3- cyclohexyl -4- hydroxy phenyl) propane, 2,2-
Bis- (3- allyl -4- hydroxy phenyl) propane；Oreinol diphenol, 5- ethyl resorcinol, 5- propyl diphenol, 5- fourth
Base resorcinol, 5- tert-butyl resorcin, 5- phenyl resorcinol, 5- cumyl resorcinol, 2,4,5,6- tetrafluoro isophthalic two
Any one in phenol, 2,4,5,6- tetrabromo resorcinol or catechol.
In the present invention, the additive amount of curing accelerator is preferably the 0.2 of every molar equivalent polyamic acid ester repetitive
~4 times.
Preferably, further include 0.2~2 part of tackifier in the negative polyimide composition, for example, can be 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 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts,
1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts etc..
Preferably, the tackifier include bis- (2- ethoxy) -3-aminopropyltriethoxysilane, N, bis- (the 2- hydroxyls of N-
Ethyl)-N, bis- (trimethoxy-silylpropyl) ethylene diamines of N-, vinyltriethoxysilane, N- (methylol)-N-
Dimethylaminopropyl trimethoxy silane, 7- triethoxysilylpropoxy -5- flavonol, N- (3- triethoxy first
Ethoxysilylpropyl) -4- hydroxybutyrate amide, 2- hydroxyl -4- (3 methyl diethoxy silicyl propoxyl group) diphenylketone, 1,3-
Bis- (4- hydroxyl butyl) tetramethyl disiloxanes, 3- (N- acetyl group -4- hydroxy propyloxy group) propyl-triethoxysilicane or hydroxyl first
In ethyl triethoxy silicane alkane any one or at least two combination；Preferably bis- three second of (2- ethoxy) -3- aminopropyl
Oxysilane.
Preferably, further include 0.4~3 part of levelling agent in the negative polyimide composition, for example, can be 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 or 3
Part etc..
In the present invention, those skilled in the art may be selected common levelling agent and be added, it is preferable to use acrylate
Substance is controlled between 6000-20000 as levelling agent, number-average molecular weight, and molecular weight distribution is narrow, glass transition temperature
Control is at -20 DEG C hereinafter, surface tension 25-26mN/m or less.
Fourth aspect, the negative polyimide composition that the present invention provides a kind of as described in the third aspect is in electronical display
Application in device.
Compared with the existing technology, the invention has the following advantages:
Poly amic acid ester provided by the invention, by introducing ester bond or amido bond on the side chain of polymer repeat unit,
The solidification temperature and dielectric constant that polyimides can be significantly reduced, compared to the polyamic acid that side chain is not modified, negative
In property polyimide compositions, can directly at 200 DEG C and it is following solidified, and dielectric constant can reach 3 hereinafter, even may be used
Reach 2 hereinafter, shortening process time, reduction power consumption is better able to adapt to the requirement of semi-conductor industry, have a extensive future.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the poly amic acid ester that the embodiment of the present invention 1 provides.
Fig. 2 is the GPC result figure for the poly amic acid ester that the embodiment of the present invention 1 provides.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of poly amic acid esters
Wherein R3For the combination of methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane-based, than
Example is 9:1.
In stirring, 4,4'- diaminodiphenyl ether (0.29mol) is added in pyromellitic dianhydride (0.3mol), 25
DEG C continue stirring 2 hours, a small amount of methacrylic acid -2- hydroxy methacrylate is then added into reaction mixture, is still deposited with combining
End position anhydride group.After stirring at 30 °C for 2 hours, the methacrylic acid contracting of 0.54mol is added into reaction mixture
Water glyceride and 0.06mol aminopropyl isobutyl group silsesquioxane and suitable benzyl dimethylamine and hydroquinone.Then, will
Solution is heated to 60 DEG C of temperature, stirs 23 hours, is then added drop-wise in ethyl alcohol, is vigorously stirred simultaneously.The sediment quilt of formation
It extracts out and is dried in a vacuum at room temperature, obtain poly amic acid ester, n value is 178.
The infrared results figure of poly amic acid ester as shown in Figure 1, smoothly connect as shown in Figure 1, in reaction process siloxy in
POSS base.
Fig. 2 is the result figure of GPC, as seen from the figure, weight average molecular weight 75367.
Embodiment 2
The present embodiment provides a kind of poly amic acid esters
Wherein R3For the combination of methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane-based, than
Example is 5:1.
In stirring, 4,4'- diaminodiphenyl ether (0.6mol) is added in pyromellitic dianhydride (0.6mol), at 25 DEG C
Continue stirring 2 hours, methacrylic acid -2- hydroxy methacrylate is then added into reaction mixture, to combine the end still having
Position anhydride group.After being stirred at room temperature 2 hours, into reaction mixture be added 1mol glycidyl methacrylate and
0.2mol aminopropyl isobutyl group silsesquioxane and suitable benzyl dimethylamine and hydroquinone.Then, solution is heated to
60 DEG C of temperature stirs 23 hours, is then added drop-wise in ethyl alcohol, is vigorously stirred simultaneously.The sediment of formation is extracted and in room
It is dried in a vacuum under temperature, obtains poly amic acid ester, n value is 120, weight average molecular weight 50788.
Embodiment 3
The present embodiment provides a kind of poly amic acid esters
Wherein R3For the combination of methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane-based, than
Example is 9:1.
In stirring, 4,4'- diaminodiphenyl ether is added into the double phthalic anhydrides (0.3mol) of 4,4'- oxygen
(0.29mol) continues stirring 2 hours at 30 DEG C, a small amount of methacrylic acid -2- hydroxyl second is then added into reaction mixture
Ester, to combine the end still having position anhydride group.After stirring at 30 °C for 2 hours, 0.54mol is added into reaction mixture
Glycidyl methacrylate and 0.06mol aminopropyl isobutyl group silsesquioxane and suitable benzyl dimethylamine and right
Benzenediol.Then, solution is heated to 60 DEG C of temperature, is stirred 23 hours, is then added drop-wise in ethyl alcohol, is vigorously stirred simultaneously.
The sediment of formation is extracted and is dried in a vacuum at room temperature, obtains poly amic acid ester, and n value is 170, and weight average molecular weight is
71983。
Embodiment 4
The present embodiment provides a kind of poly amic acid esters
Wherein R3For the combination of methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane-based, than
Example is 7:1.
In stirring, to4,4'- diaminodiphenyl ether is added in (0.3mol)
(0.29mol) continues stirring 2 hours at 30 DEG C, a small amount of methacrylic acid -2- hydroxyl second is then added into reaction mixture
Ester, to combine the end still having position anhydride group.After stirring at 30 °C for 2 hours, it is added into reaction mixture
The glycidyl methacrylate and 0.075mol aminopropyl isobutyl group silsesquioxane of 0.525mol and suitable benzyl
Dimethylamine and hydroquinone.Then, solution is heated to 60 DEG C of temperature, stirs 23 hours, is then added drop-wise in ethyl alcohol, simultaneously
It is vigorously stirred.The sediment of formation is extracted and is dried in a vacuum at room temperature, obtains poly amic acid ester, and n value is 180, weight
Average molecular weight is 76217.
Comparative example 1
The difference of this comparative example and embodiment 1 is only that, R3For methacrylic acid -2- hydroxyl n-propyl base, that is, reacted
Feed intake all glycidyl methacrylate in journey.
Comparative example 2
The difference of this comparative example and embodiment 1 is only that, R3For aminopropyl isobutyl group silsesquioxane-based, i.e. reaction process
In feed intake all aminopropyl isobutyl group silsesquioxanes.
Comparative example 3
The difference of this comparative example and embodiment 1 is only that, R3For hydrogen, i.e., without the esterification of second stage in reaction process
Reaction.
Embodiment 7
The present embodiment provides a kind of negative polyimide compositions, by weight include following components:
30 parts of poly amic acid ester of the offer of embodiment 1,16 parts of oxime ester compound, dimethacrylate tetraethylene-glycol ester
15 parts, 2 parts of quinoline, 1 part of -3-aminopropyltriethoxysilane of bis- (2- ethoxys), and 1 part of levelling agent, N- methyl -2- pyrrolidines
40 parts of ketone.
Embodiment 8
The present embodiment provides a kind of negative polyimide compositions, by weight include following components:
35 parts of poly amic acid ester of the offer of embodiment 2,2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-1- acetone
20 parts, 20 parts of dimethacrylate, 5 parts of γ-aminobutyric acid, 2 parts of vinyltriethoxysilane, levelling agent 3
Part, 60 parts of dimethyl sulfoxide.
Embodiment 9
The present embodiment provides a kind of negative polyimide compositions, by weight include following components:
40 parts of poly amic acid ester, N of the offer of embodiment 3,10 parts of N'- tetramethyl -4,4'- diaminobenzophenone, three hydroxyls
10 parts of dimethacrylate, 1 part of benzdioxan, 1,3- 0.2 part of tetramethyl disiloxane of bis- (4- hydroxyl butyl),
0.4 part of levelling agent, 40 parts of tetramethylurea.
Embodiment 10
The present embodiment provides a kind of negative polyimide compositions, by weight include following components:
26 parts of poly amic acid ester of the offer of embodiment 4,13 parts of benzophenone, 14 parts of 4-vinylpridine, 3 parts of glutamic acid,
1,3- 0.7 part of tetramethyl disiloxane, 1.2 parts of levelling agent, 35 parts of hexamethylphosphoric triamide of bis- (4- hydroxyl butyl).
Comparative example 4
This comparative example provides a kind of negative polyimide composition, by weight includes following components:
30 parts of poly amic acid ester of the offer of comparative example 2,16 parts of oxime ester compound, dimethacrylate tetraethylene-glycol ester
15 parts, 2 parts of quinoline, 1 part of -3-aminopropyltriethoxysilane of bis- (2- ethoxys), and 1 part of levelling agent, N- methyl -2- pyrrolidines
40 parts of ketone.
Comparative example 5
This comparative example provides a kind of negative polyimide composition, by weight includes following components:
30 parts of poly amic acid ester of the offer of comparative example 3,16 parts of oxime ester compound, dimethacrylate tetraethylene-glycol ester
15 parts, 2 parts of quinoline, 1 part of -3-aminopropyltriethoxysilane of bis- (2- ethoxys), and 1 part of levelling agent, N- methyl -2- pyrrolidines
40 parts of ketone.
Comparative example 6
This comparative example provides a kind of negative polyimide composition, by weight includes following components:
30 parts of poly amic acid ester of the offer of comparative example 4,16 parts of oxime ester compound, dimethacrylate tetraethylene-glycol ester
15 parts, 2 parts of quinoline, 1 part of -3-aminopropyltriethoxysilane of bis- (2- ethoxys), and 1 part of levelling agent, N- methyl -2- pyrrolidines
40 parts of ketone.
The negative polyimide composition that above-described embodiment 7-10 and comparative example 4-6 are provided carries out the solidification of imidizate
Temperature test (passing through infrared test) and dielectric constant (impedance instrument) test, the concrete outcome of test are as shown in table 1 below:
Table 1
| Sample | Amination rate (%) | Dielectric constant |
| Embodiment 7 | 98.6 | 2.2 |
| Embodiment 8 | 98.4 | 2.4 |
| Embodiment 9 | 98.3 | 2.1 |
| Embodiment 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 shown in Table 1, if R3Appropriateness is carried out without using aminopropyl isobutyl group silsesquioxane in group to be modified,
Then the dielectric properties of negative polyimide composition are poor, and dielectric constant can be 3 or more；And work as R3It is different using aminopropyl in group
After butyl silsesquioxane is modified, dielectric properties are greatly promoted, and dielectric constant generally can reach 2 or so.
In addition, the dosage of aminopropyl isobutyl group silsesquioxane will guarantee that appropriateness is modified, by infrared spectrum analysis
It is found with morphology characterization, as the content of POSS increases, will lead to viscosity and steeply rise, side group increases wrapped around one another, leads to sky
Hole becomes larger, and hydroscopicity rises, dielectric properties decline；Therefore its dosage general control be and other esterifying reagents ratio be 1:(7~
9) when, dielectric properties be can reach most preferably.
The Applicant declares that the present invention is explained by the above embodiments poly amic acid ester of the invention, preparation method and
Negative polyimide composition and application, but the invention is not limited to above-mentioned processing steps, that is, do not mean that the present invention is necessary
Relying on above-mentioned processing step could implement.It should be clear to those skilled in the art, any improvement in the present invention, right
The equivalence replacement of raw material selected by the present invention and addition, the selection of concrete mode of auxiliary element etc., all fall within guarantor of the invention
It protects within range and the open scope.
Claims (10)
1. a kind of poly amic acid ester, which is characterized in that the structure of the poly amic acid ester is shown in formula I:
Wherein, R1For quadrivalent organic radical group, R2For bivalent organic group, R3For C1~C20Alkyl, C3~C20Naphthenic base or contain
Have in the monovalent organic group of acrylate structural any one or at least two combination and aminopropyl isobutyl group sesquialter silicon
The combination of oxyalkyl；The value of n is 150~300.
2. poly amic acid ester according to claim 1, which is characterized in that the R1For In any one, wherein dotted line indicate in formula
The on-position of group in I, X are oxygen atom, sulphur atom, sulfonyl, carbonyl, full aryl polysiloxane, the substitution of unsubstituted or fluorine
Aliphatic group, any one in aryl radical or alkyl, R4And R5Independently selected from unsubstituted or fluorine-substituted aliphatic hydrocarbon
Base；
Preferably, the R2ForWherein dotted line indicates the on-position of the group in Formulas I, and Y is oxygen
Atom, sulphur atom, alkyl, sulfonyl, carbonyl, full aryl polysiloxane, unsubstituted or fluorine-substituted aliphatic group, aryl radical
Or any one in fragrant two ethers；
Preferably, the R3For the monovalent organic group containing acrylate structural and aminopropyl isobutyl group silsesquioxane-based
Combination.
3. poly amic acid ester according to claim 1 or 2, which is characterized in that the R1ForWherein dotted line table
Show the on-position of the group in Formulas I；
Preferably, the R2ForWherein dotted line indicates the on-position of the group in Formulas I；
Preferably, the R3For the combination of methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group silsesquioxane-based；
Preferably, in the structure shown in 1mol Formulas I, methacrylic acid -2- hydroxyl n-propyl base and aminopropyl isobutyl group sesquialter
The molar ratio of siloxy group is (5~10): 1；Preferably (7~9): 1.
4. the preparation method of poly amic acid ester according to any one of claim 1-3, which is characterized in that the preparation side
Method is the following steps are included: compound a is mixed after the first stage reacts with compound b, addition R3A continues second-order
Duan Fanying obtains poly amic acid ester, and the structure of compound a isThe structure of compound b is H2N-R2-NH2, A is-OH
Or-NH2, wherein R1、R2And R3It is identical as the range limited in claim 1.
5. the preparation method according to claim 4, which is characterized in that compound a, compound b and R3The molar ratio of A is 1:
(0.8~1): (2~2.2)；
Preferably, the temperature of the first stage reaction is 20~40 DEG C；
Preferably, the time of the first stage reaction is 1~5h；
Preferably, the second stage reaction carries out in the presence of catalyst and polymerization inhibitor；
Preferably, the catalyst is benzyl dimethylamine；
Preferably, the polymerization inhibitor is hydroquinone and/or quinhydrones；
Preferably, the temperature of the second stage reaction is 30~60 DEG C；
Preferably, the time of second stage reaction be 10~for 24 hours.
6. a kind of negative polyimide composition, which is characterized in that the negative polyimide composition includes by weight
Following components: 20~40 parts of poly amic acid ester of any of claims 1-3,10~20 parts of photoinitiator, photo-crosslinking
10~20 parts of agent, 1~5 part of curing accelerator, 35~60 parts of solvent.
7. negative polyimide composition according to claim 6, which is characterized in that the photoinitiator includes oxime esterification
Close object, benzophenone, N, N'- tetramethyl -4,4'- diaminobenzophenone, 2- benzyl -2- dimethylamino -1- (4- morpholine benzene
Base) butanone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-1- acetone, alkyl-anthraquinone, benzoin alkylether, benzene idol
In relation by marriage, alkyl benzoin or benzil dimethyl ketal any one or at least two combination, preferably oxime ester compound
And benzophenone；
Preferably, the photocrosslinking agent includes dimethacrylate tetraethylene-glycol ester, diethylene glycol diacrylate, three second
Omega-diol diacrylate, tetraethylene glycol diacrylate, dimethacrylate, triethylene glycol dimethacrylate
Ester, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane trimethacrylate, three hydroxyl first
Base propane dimethylacrylate, trimethylol-propane trimethacrylate, 1,4 butanediol diacrylate, 1,6- oneself two
Alcohol diacrylate, 1,4- butanediol dimethylacrylate, 1,6-HD dimethylacrylate, three propylene of pentaerythrite
Acid esters, pentaerythritol tetraacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, styrene,
Divinylbenzene, 4- vinyltoluene, 4-vinylpridine, n-vinyl pyrrolidone, 2-hydroxyethyl methacrylate, third
Olefin(e) acid 2- hydroxy methacrylate, 1,3- acryloxy -2- hydroxy propane, 1,3- methacryloxy -2- hydroxy propane, methylene
Bisacrylamide, N, in N- dimethylacrylamide, N hydroxymethyl acrylamide any one or at least two combination；It is excellent
It is selected as dimethacrylate tetraethylene-glycol ester；
Preferably, the solvent includes n-methyl-2-pyrrolidone, n,N-dimethylacetamide, n,N-Dimethylformamide, two
In methyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide or gamma-butyrolacton any one or at least two combination.
8. negative polyimide composition according to claim 6 or 7, which is characterized in that the curing accelerator includes
Contain nitrogen, carbonyl or extremely outside substituted or unsubstituted nitrogen-containing heterocycle compound, substituted or unsubstituted amino acids, ring
In the aromatic compound of few two hydroxyls any one or at least two combination；
Preferably, the pKa value of the nitrogen-containing heterocycle compound in water is 0~8；
Preferably, the nitrogen-containing heterocycle compound include imidazoles, pyrazoles, triazole, tetrazolium, benzimidazole, naphtho- imidazoles, indazole,
Benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinolin, bipyridyl, two quinolyls, pyridazine, pyrimidine, pyrrole
Piperazine, 2,3- benzodiazine, quinoxaline, quinazoline, cinnolines, naphthyridines, acridine, phenanthridines, benzene quinoline, benzisoquinoline, benzoquinoline,
Benzo phthalazines, Benzoquinoxalines, Benzoquinazole, phenanthroline, azophenlyene, carboline, pyrimidine, triazine, tetrazine, pteridine, oxazole, benzo
Oxazole, isoxazole, benzo isoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazoles, thiadiazoles, pyrrolidines two
Any one in ketone, isoindoledione, pyrrolidine-diones, benzene isoquinolin diketone, triethylenediamine or hexa；
Preferably, the amino acids include glycine, sarcosine, dimethylglycine, glycine betaine, alanine, α-
Aminobutyric acid, beta-aminobutyric acid, γ-aminobutyric acid, gamma-amino-β-ketobutyric acid, valine, beta-amino isovaleric acid, γ-ammonia
Base isoamyl, go first valine, beta-amino valeric acid, gamma-amino valeric acid, δ-aminovaleric acid, leucine, isoleucine, nor-leucine,
Serine, Alpha-Methyl serine, isoerine, Alpha-Methyl isoerine, seromycin, homoserine, threonine, adjacent methyl Soviet Union
Propylhomoserin, isothreonine, adjacent methyl isothreonine, trans- -3- cyclohexane-carboxylic acid, cis- -3- cyclohexanecarboxylic acid, ε-amine oneself
Acid, omega-amino dodecanoic acid, beta-hydroxy valine, beta-hydroxy isoleucine, Alpha-hydroxy-beta-amino isovaleric acid, ε-diazonium-δ-
Oxo leucine, alpha-amido-ε-hydroxyl amino caproic acid, cysteine, cystine, S- methyl cysteine, half Guang ammonia of S- methyl
Acid-S- oxide, cysteine, homocysteine, homocystine, methionine, penicillamine, taurine, α, β-diaminopropionic acid,
Ornithine, lysine, arginine, canaline, canavanine, δ-hydroxylysine, aspartic acid, asparagine, isoasparagine,
Glutamic acid, glutamine, isoglutamine, Alpha-Methyl glutamic acid, beta-hydroxyglutamic acid, γ-Hydroxy GIutaminic Acid, alpha-amido oneself two
Acid, citrulling, lanthionine, cystathionie, phenylalanine, Alpha-Methyl phenylalanine, o- chlorophenylalanine, the third ammonia of m- chlorobenzene
Acid, fenclonine, adjacent fluorophenylalanine, fluorophenylalanine, P-fluoropnenylalanine, β-(2- pyridyl group) alanine, junket
Propylhomoserin, thyroxine, dichloro tyrosine, bromotiren, diiodotyrosine, 3,4- dihydroxyphenylalanine, Alpha-Methyl -3,4-
Dihydroxyphenylalanine, phenylglycine, tryptophan, abrine, histidine, 1-Methyl histidine, 2-Thiolhistidine, dried meat
Propylhomoserin, hydroxy-proline, ortho-aminobenzoic acid, p-aminobenzoic acid, 2-Thiolhistidine, proline, hydroxyproline or adjacent ammonia
Any one in yl benzoic acid；
Preferably, the aromatic compound include benzene, anthraquinone, phenanthrenequione, Fluorenone, pyrroles, indoles, iso-indoles, carbazole, furans,
Coumarone, isobenzofuran, thiophene, benzothiophene, dibenzothiophenes, benzodioxole, benzdioxan, biphenyl,
Acetophenone, propiophenone, butyrophenone, benzophenone, benzoic ether, benzene dicarboxylic acid diester, benzamide, benzonitrile, benzaldehyde, nitre
Base benzene, benzene sulfonic acid, aniline, diphenylamines, diphenyl methylamine, triphenylamine, triphenylmenthane, triphenylcarbinol, diphenyl methylene hexamethylene two
Ketenes, 4,4' dihydroxy diphenyl, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, bis- (4- hydroxy phenyl) methane, bis- (4- hydroxy benzenes
Base) diphenyl methane, bis- (4- hydroxy phenyl) -1- naphthyl methanes, bis- (4- hydroxy phenyl) ethane of 1,2-, bis- (the 4- hydroxyls of 1,1-
Phenyl) -1- diphenylphosphino ethane, 2- (4- hydroxy phenyl) -2- (3- hydroxy phenyl) propane, bis- (4- hydroxy phenyl) phenylmethanes, 2,
Bis- (4- hydroxyl -3- bromophenyl) propane of 2-, bis- (hydroxy phenyl) pentamethylene of 1,1-, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 1,
Bis- (4- hydroxy phenyl) isobutenes of 1-, bis- (4- hydroxy phenyl) cyclododecanes of 1,1-, bis- (4- the hydroxy phenyl) -2- of trans- -2,3-
Butylene, 2,2- bis- (4- hydroxy phenyl) adamantane, α, bis- (4- hydroxy phenyl) toluene of α '-, bis- (4- hydroxy phenyl) acetonitriles, 2,2-
Bis- (3- ethyl -4- hydroxy phenyl) propane of bis- (3- methyl -4- hydroxy phenyl) propane, 2,2-, the bis- (3- n-propyl -4- hydroxyls of 2,2-
Base phenyl) propane, bis- (3- isopropyl -4- hydroxy phenyl) propane of 2,2-, bis- (3- sec-butyl -4- hydroxy phenyl) propane of 2,2-,
Bis- (3- cyclohexyl -4- hydroxy phenyl) propane of bis- (3- tert-butyl-hydroxy phenyl) propane of 2,2-, 2,2-, bis- (the 3- allyls of 2,2-
Base -4- hydroxy phenyl) propane；Oreinol diphenol, 5- ethyl resorcinol, 5- propyl diphenol, 5- butyl isophthalic two
Phenol, 5- tert-butyl resorcin, 5- phenyl resorcinol, 5- cumyl resorcinol, 2,4,5,6- tetrafluoro resorcinol, 2,4,5,
Any one in 6- tetrabromo resorcinol or catechol.
9. negative polyimide composition a method according to any one of claims 6-8, which is characterized in that the negativity polyamides
It further include 0.2~2 part of tackifier in imines composition；
Preferably, the tackifier include bis- (2- ethoxy) -3-aminopropyltriethoxysilane, N, bis- (the 2- hydroxyl second of N-
Base)-N, bis- (trimethoxy-silylpropyl) ethylene diamines of N-, vinyltriethoxysilane, N- (methylol)-N- first
Base TSL 8330,7- triethoxysilylpropoxy -5- flavonol, N- (3- triethoxy first silicon
Alkyl propyl) -4- hydroxybutyrate amide, 2- hydroxyl -4- (3 methyl diethoxy silicyl propoxyl group) diphenylketone, 1,3- be bis-
(4- hydroxyl butyl) tetramethyl disiloxane, 3- (N- acetyl group -4- hydroxy propyloxy group) propyl-triethoxysilicane or hydroxymethyl
In triethoxysilane any one or at least two combination；Preferably bis- three ethoxies of (2- ethoxy) -3- aminopropyl
Base silane；
It preferably, further include 0.4~3 part of levelling agent in the negative polyimide composition.
10. application of the negative polyimide composition in electron display device according to any one of claim 6-9.
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| CN115181268A (en) * | 2022-06-29 | 2022-10-14 | 深圳职业技术学院 | Photosensitive polyimide, process for producing the same, and photosensitive polyimide composition |
| WO2023202454A1 (en) * | 2022-04-19 | 2023-10-26 | 上海交通大学 | Polymer for black matrix, and preparation method therefor and use thereof |
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| CN115181268A (en) * | 2022-06-29 | 2022-10-14 | 深圳职业技术学院 | Photosensitive polyimide, process for producing the same, and photosensitive polyimide composition |
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