CN101117384A - Forerunner of polyimide and uses thereof - Google Patents
Forerunner of polyimide and uses thereof Download PDFInfo
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- CN101117384A CN101117384A CNA2007101380633A CN200710138063A CN101117384A CN 101117384 A CN101117384 A CN 101117384A CN A2007101380633 A CNA2007101380633 A CN A2007101380633A CN 200710138063 A CN200710138063 A CN 200710138063A CN 101117384 A CN101117384 A CN 101117384A
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Abstract
The present invention provides a polyimide precursor with a concrete structure, wherein, R, Rx, G, P and m are as defined hereinabove. The present invention also provides polyimide that is produced by the precursor, and also has good operating straits and good physical and chemical properties.
Description
Technical field
The present invention relates to a kind of precursor of novel polyimide, the present invention is also about the application in preparation polyimide (polyimide is called for short PI) of the precursor of described novel polyimide.
Background technology
Polyimide is the first-selection of high performance polymer material owing to having excellent heat-resistant quality and favorable mechanical, electric and chemical property always.In addition, because the requirement of semi-conductor on characteristic is more and more higher, and traditional inorganic materials has its limit and shortcoming of using, and the characteristic of polyimide just can remedy the weak point of traditional material in some aspects.Therefore, after E.I.Du Pont Company develops the aromatic polyimide technology, promptly be subjected to noting widely, and develop and the multiduty polyimide of many tools.
On semi-conductor industry, polyimide is widely used in aspects such as passive film, stress buffer film, alpha-particle shielding film, dry-etching shield cap, micro electronmechanical and interlayer dielectric, and develops other new purposes just successively.Wherein, the great majority application is as protecting filming of integrated circuit component, because of polyimide material can be by the test of integrated circuit component reliability.But the application of polyimide is not only at integrated circuit industry, and it is all quite important on electronic packaging, enameled wire, printed circuit board (PCB), sensing element, separatory membrane and structured material, is playing the part of the role of key material.
Generally be to adopt the polymerization condensation reaction mode of two-stage to come synthesis of polyimides.Wherein, usually diamine monomer is dissolved in polarity as N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO), the non-protonic solvent in the fs, again mole of diacid anhydride monomer such as adding., under low temperature or normal temperature carry out condensation reaction, form polyimide precursor (precursor) thereafter, that is, and polyamic acid (poly (amicacid); Abbreviate PAA as).
Then, carry out subordinate phase, carry out the reaction of condensation cyclodehydration, change polyamic acid into polyimide by the imidization (thermal imidization) of type of heating or the imidization (chemical imidization) of chemical mode.
The reaction process of preparation polyimide can be summarized as follows at present:
In above-mentioned preparation method,, behind imidization (imidization), can't obtain the polyimide film of tool good physical so if the polyamic acid molecular weight of fs gained does not reach certain standard (that is, molecular weight is too small).Yet,,, so that the operability variation, be easy to when coating, have shortcomings such as levelling property is bad just its viscosity can be too big so if the molecular weight of fs gained polyamic acid is too high.Say it for example, when being rotated coating, being easy to generate convexity and webbing etc. and being difficult for the levelling phenomenon.In addition, too high polyamic acid molecular weight will be when carrying out the imidization of subordinate phase, because of intermolecular interaction and molecular chain bond distance's shortening produces very big internal stress, causes institute's substrates coated flexural deformation.Therefore, for exempting foregoing problems, extensively inquire into the heating gradient curve and the internal stress relation of subordinate phase imidization on the document already, and work out the mode of various reduction internal stress.Yet aforementioned levelling property and internal stress problem are traced it to its cause, all because of fs gained polyamic acid molecular weight too high due to.In other words, if can properly control the polyamic acid molecular weight, just the polyimide film of the good physical property of tool can be provided.
In addition, polyamic acid moisture absorption quite easily, and then polyamic acid is degraded with water molecule reaction, so be difficult for preservation.
The problems referred to above continue perplexing the personnel that are engaged in polyimide research for many years, conflict because often exist between material behavior and the operability, so can't get both.The research and development achievement that the present invention promptly does at foregoing problems by special synthesis mode, can taken into account under the situation of operability, and the polyimide film of physical property that tool is wanted is provided, and meets the demand of industry.
Summary of the invention
A purpose of the present invention is to provide a kind of precursor of polyimide of novelty.
Another object of the present invention is to provide a kind of composition that comprises above-mentioned precursor.
Another purpose of the present invention is to provide a kind of method for preparing polyimide.
Description of drawings
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Embodiment
The precursor of polyimide of the present invention is the amic acid esters oligomer of the structure of tool following formula (1):
Wherein
R is that the straight or branched alkyl of 1 to 14 carbon atom of tool, the aryl or aralkyl or the ethene of 6 to 14 carbon atoms of tool are unsaturated group;
R
xBut independent separately is H or sensitization polymeric group;
G independently is the organic group of 4 valencys separately;
P independently is the organic group of divalent separately; And
M is 0 to 100 integer.
According to concrete enforcement of the present invention aspect, the R in the above-mentioned formula (1) is the straight or branched alkyl of 1 to 14 carbon atom of tool, and it for example is the straight or branched alkyl of the following structure of tool:
Wherein n is 0 to 10 integer.The specific examples of the straight or branched alkyl of 1 to 14 carbon atom of described tool is including (but not limited to) methyl, ethyl, n-propyl, sec.-propyl, 1-methyl-propyl, 2-methyl-propyl, normal-butyl, isobutyl-(isobutyl), the tertiary butyl (tert-butyl), 1-methyl butyl, 2-methyl butyl, amyl group, hexyl, heptyl and octyl group etc.
The aryl or aralkyl of 6 to 14 carbon atoms of aforementioned tool is preferably and is selected from the group that is made of following groups:
Above-mentioned ethene is unsaturated group, there is no particular restriction, the example includes, but is not limited to vinyl, propenyl, methylpropenyl, n-butene base, isobutenyl, ethenylphenyl, propenyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group, reaches metacryloxy hexyl and group as the formula (2)
Wherein, R
1For stretching phenyl, C
3-C
8Stretch the C of cycloalkyl, straight or branched
1-C
8Stretch alkyl, C
1-C
8Stretch thiazolinyl or C
1-C
8Hydroxyl is stretched alkyl, and R
2Be hydrogen or C
1-C
4Alkyl.Wherein, preferable formula (2) group can be:
Radicals R in the above-mentioned formula (1)
xBut can be separately independent for H or anyly have sensitization polymeric group, but described sensitization polymeric group be preferably the group that the ethene that contains as hereinbefore defined is unsaturated group.According to the present invention, radicals R
x-preferable independence separately is H, methacrylic acid-2-hydroxy propyl ester base, Jia Jibingxisuanyizhi base, ethyl propenoate base, propenyl, methylpropenyl, n-butene base or isobutenyl, and better is H or methacrylic acid-2-hydroxy propyl ester base independently separately:
The 4 valency organic group G that formula of the present invention (1) amic acid esters oligomer is contained there is no particular restriction, and it for example is the aromatic group of 4 valencys or the aliphatic group of 4 valencys.Aforementioned aromatic group can be monocycle or many rings, is preferably and is selected from the group that is made of following groups:
Wherein Y independently is hydrogen, halogen, C separately
1-C
4Perfluoroalkyl or C
1-C
4Alkyl, and B is-CH
2-,-O-,-S-,-CO-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-; Be more preferred from and be selected from the group that constitutes by following groups:
According to the present invention, the group that the optional free following groups of above-mentioned 4 valency fatty groups is constituted:
The divalent organic group P that formula of the present invention (1) amic acid esters oligomer is contained there is no particular restriction, it typically is aromatic group, preferablely independently is separately
Wherein, X independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; A is-O-,-S-,-CO-,-CH
2-,-OC (O)-or-CONH-.More preferably, described divalent organic group P independently is separately
In aspect a preferable concrete enforcement, described divalent organic group P is
Above-mentioned divalent organic group P also can be the non-aromatic group, for example:
Wherein, X such as preamble define; And respectively do for oneself 1 to 3 integer of w and z, preferably, described divalent organic group P is
This case contriver finds, be different from the polyamic acid precursor of prior art in order to the preparation polyimide, above-mentioned formula (1) amic acid esters oligomer is because the acidic group minimizing, so more can moisture absorption, even moisture absorption, also comparatively stable, so can at room temperature preserve standbyly, need not to be stored under the low temperature (as: subzero 20 ℃).
Amic acid esters oligomer of the present invention can obtain by the known polymerization process of the technician who has general knowledge in the technical field of the invention, for example can make by the method that comprises the following step:
(a) dicarboxylic anhydride of tool following formula (3) and the compound (R-OH) of tool hydroxyl are reacted, form the compound of tool following formula (4); And
(b) in step (a) product, add tool formula H
2N-P-NH
2Diamine compound, form formula (5) amic acid esters oligomer.
(c) but add according to circumstances and have sensitization polymer-based group (R
*) monomer, for example epoxy acrylate (epoxyacrylate) reacts, and forms formula (6) amic acid esters oligomer,
Wherein R, G and P such as preamble define, a, b, and f respectively do for oneself 0 to 100 integer and a+b≤100.
In the method for above-mentioned preparation formula (1) amic acid esters oligomer; the employed dicarboxylic anhydride of step (a) generally can be aliphatics or aromatic series person, is preferably the aromatic diacid acid anhydride; the example includes, but is not limited to pyromellitic acid dianhydride (PMDA); 4; 4 '-two phthalandione dianhydrides (BPDA); 4,4 '-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA); 1-(trifluoromethyl)-2,3; 5; 6-benzene tertacarbonic acid dianhydride (P3FDA); benzophenone-tetracarboxylic dianhydride (BTDA); 3,3 ', 4; 4 '-phenyl ether tetracarboxylic dianhydride (ODPA); 1; two (trifluoromethyl)-2,3 of 4-, 5; 6-benzene tertacarbonic acid dianhydride (P6FDA); 1-(3 '; 4 '-the dicarboxyl phenyl)-1,3,3-trimethylammonium indane-5; the 6-dicarboxylic acid dianhydride; 1-(3 '; 4 '-the dicarboxyl phenyl)-1,3,3-trimethylammonium indane-6; the 7-dicarboxylic acid dianhydride; 1-(3 '; 4 '-the dicarboxyl phenyl)-3-methyl indan-5, the 6-dicarboxylic acid dianhydride; 1-(3 ', 4 '-the dicarboxyl phenyl)-3-methyl indan-6; the 7-dicarboxylic acid dianhydride; 2; 3,9,10-perylene tetracarboxylic dianhydride; 1; 4; 5,8-naphthalene tetracarboxylic acid dianhydride; 2,6-dichloronaphtalene-1; 4; 5, the 8-tetracarboxylic dianhydride; 2,7-dichloronaphtalene-1; 4; 5, the 8-tetracarboxylic dianhydride; 2,3; 6; 7-Tetrachloronaphthalene-2,4,5; the 8-tetracarboxylic dianhydride; luxuriant and rich with fragrance-1; 8,9, the 10-tetracarboxylic dianhydride; 3; 3 '; 4,4 '-benzophenone tetracarboxylic dianhydride; 1,2 '; 3; 3 '-benzophenone tetracarboxylic dianhydride; 3,3 ', 4; 4 '-biphenyl tetracarboxylic dianhydride; 3; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride; 2; 2 '; 3,3 '-biphenyl tetracarboxylic dianhydride; 4,4 '-isopropylidene two phthalandione dianhydrides; 3; 3 '-isopropylidene two phthalandione dianhydrides; 4; 4 '-oxygen base two phthalandione dianhydrides; 4,4 '-alkylsulfonyl two phthalandione dianhydrides; 3,3 '-oxygen base two phthalandione dianhydrides; 4; 4 '-methylene radical two phthalandione dianhydrides; 4; 4 '-sulfenyl two phthalandione dianhydrides; 4,4 '-ethylene phthalandione dianhydride; 2,3; 6; 7-naphthalene tetracarboxylic acid dianhydride; 1,2,4; 5-naphthalene tetracarboxylic acid dianhydride; 1; 2,5,6-naphthalene tetracarboxylic acid dianhydride; benzene-1; 2; 3, the 4-tetracarboxylic dianhydride; pyridine-2,3; 5,6-tetracarboxylic dianhydride or its combination.
Preferably, in step (a), adopt the aromatic diacid acid anhydride that is selected from following group: pyromellitic acid dianhydride (PMDA), 4,4 '-two phthalandione dianhydrides (BPDA), 4,4 '-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P3FDA), 1, two (trifluoromethyl)-2,3 of 4-, 5,6-benzene tertacarbonic acid dianhydride (P6FDA), benzophenone-tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA) and its mixture.Adopt pyromellitic acid dianhydride (PMDA) in aspect a concrete enforcement.
Can be used for the inventive method and can be alcohols with the compound of the tool hydroxyl of preparation formula (1) amic acid esters oligomer, for example monohydroxy-alcohol, dibasic alcohol or polyvalent alcohol are preferably monohydroxy-alcohol.Can be used for monohydroxy-alcohol of the present invention and there is no special restriction, it can be alkyl alcohol, aralkyl alcohol or aryl alcohol.Say it (but not as limit) for example, described monohydroxy-alcohol can be the straight or branched alkyl alcohol of 1 to 14 carbon atom of tool, for example the straight or branched alkyl alcohol of the following structure of tool:
Wherein, n is 0 to 10 integer.So the straight or branched alkyl alcohol of 1 to 14 carbon atom of described tool includes, but is not limited to methyl alcohol, ethanol, n-propyl alcohol, Virahol, 1-methylpropanol, propyl carbinol, isopropylcarbinol, new butanols, 1-methyl butanol, 2-methyl butanol, amylalcohol, hexanol, enanthol and octanol.Described monohydroxy-alcohol also can be the aralkyl alcohol or the aryl alcohol of 6 to 14 carbon atoms of tool, for example aralkyl alcohol of the following structure of tool or aryl alcohol:
The compound that can be used for the tool hydroxyl in the inventive method also can have can light sensitive group, and for example ethene is unsaturated group, is preferably tool following formula (7) person:
Wherein, R
1For stretching phenyl, C
3-C
8Stretch the C of cycloalkyl or straight or branched
1-C
8Stretch alkyl, C
1-C
8Stretch thiazolinyl or C
1-C
8Hydroxyl is stretched alkyl, and R
2Be hydrogen or C
1-C
4Alkyl.Preferably, formula (7) compound is selected from following group: 2-Hydroxy ethyl acrylate (2-hydroxyethyl acrylate, HEA), methacrylic acid-2-hydroxy methacrylate (2-hydroxyethylmethacrylate, HEMA), glycidyl methacrylate (glycidyl methacrylate, GMA), glycidyl acrylate (glycidyl acrylate) and its combination.
In the method for above-mentioned preparation formula (1) polyamic acid precursor, the employed diamines of step (b) there is no particular restriction, uses aromatic diamine usually.The aromatic diamine that can be used for the inventive method is by the those skilled in the art is known.Say that for example it (but not as limit) can be selected from following group: 4; 4 '-oxydianiline (ODA); Ursol D (pPDA); between dimethyl benzidine (DMDB); between two (trifluoromethyl) benzidine (TFMB); adjacent dimethyl benzidine (oTLD); 4; 4 '-octafluoro p-diaminodiphenyl (OFB); tetrafluoro-p-phenylenediamine (TFPD); 2; 2 '-5; 5 '-tetrachloro benzidine (TCB); 3; 3 '-dichlorobenzidine (DCB); 2; 2 '-two (3-aminophenyl) HFC-236fa; 2; 2 '-two (4-aminophenyl) HFC-236fa; 4; 4 '-oxygen base-two [3-(trifluoromethyl) aniline; 3; 5-diamino phenylfluoroform (3; 5-diaminobenzotrifluoride); tetrafluoro-1; 4-stretches phenylenediamine (tetrafluorophenylene diamine); tetrafluoro--phenylenediamine stretched; 1; two (4-the amino-benzene oxygen)-2-tert.-butylbenzenes (BATB) of 4-; 2; 2 '-dimethyl-4; 4 '-two (4-amino-benzene oxygen) biphenyl (DBAPB); 2; two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAPPH) of 2-; 2; 2 '-two [4-(4-amino-benzene oxygen) phenyl] norborneol alkane (BAPN); 5-amino-1-(4 '-aminophenyl)-1; 3; 3-trimethylammonium indane; 6-amino-1-(4 '-aminophenyl)-1; 3; 3-trimethylammonium indane; 4; 4 '-methylene-bis (neighbour-chloroaniline); 3; 3 '-dichloro diphenylamine; 3; 3 '-the alkylsulfonyl pentanoic; 4; 4 '-diaminobenzophenone; 1; the 5-diaminonaphthalene; two (4-aminophenyl) diethylsilane; two (4-aminophenyl) diphenyl silane; two (4-aminophenyl) ethyl phosphine oxide; N-(two (4-aminophenyl))-N-methylamine; N-(two (4-aminophenyl))-N-phenyl amine; 4; 4 '-methylene-bis (2-aminotoluene); 4; 4 '-methylene-bis(2methoxyaniline); 5; 5 '-methylene-bis (2-amino-phenol); 4; 4 '-methylene-bis (2-aminotoluene); 4; 4 '-oxygen base two (2-anisidine); 4; 4 '-oxygen base two (2-chloroaniline); 2; 2 '-two (4-amino-phenols); 5; 5 '-oxygen base two (2-amino-phenol); 4; 4 '-sulfenyl two (2-aminotoluene); 4; 4 '-sulfenyl two (2-anisidine); 4; 4 '-sulfenyl two (2-chloroaniline); 4; 4 '-alkylsulfonyl two (2-aminotoluene); 4; 4 '-alkylsulfonyl two (2-phenetidine); 4; 4 '-alkylsulfonyl two (2-chloroaniline); 5; 5 '-alkylsulfonyl two (2-amino-phenol); 3; 3 '-dimethyl-4; 4 '-diaminobenzophenone; 3; 3 '-dimethoxy-4 '; 4 '-diaminobenzophenone; 3; 3 '-two chloro-4; 4 '-diaminobenzophenone; 4; 4 '-benzidine; between-phenylenediamine; 4; 4 '-methylene dianiline (MDA) (MDA); 4; 4 '-the sulfenyl pentanoic; 4; 4 '-the alkylsulfonyl pentanoic; 4; 4 '-the isopropylidene pentanoic; 3; 3 '-dimethoxy benzidine; 3; 3 '-dicarboxylate biphenyl amine; 2; 4-tolyl diamines; 2; 5-tolyl diamines; 2; 6-tolyl diamines; between-the xylyl diamines; 2; 4-diamino-5-toluene(mono)chloride; 2,4-diamino-6-toluene(mono)chloride; with its combination.Preferably, adopt 4,4 '-oxydianiline (ODA), Ursol D (pPDA), a dimethyl benzidine (DMDB), two (trifluoromethyl) benzidine (TFMB), adjacent dimethyl benzidine (oTLD), 4,4 '-methylene dianiline (MDA) (MDA) or its mixture.
Preferably, adopt the diamines that is selected from following group in step (b):
As described above, can be if necessary in step (c) but in add and have the monomer of sensitization polymer-based group, but make gained amic acid esters oligomer have sensitization polymeric group.
In specific words, but when interpolation does not have the monomer of sensitization polymer-based group, the R in gained formula (1) the amic acid esters oligomer
xBe H; And when but interpolation has the monomer of sensitization polymer-based group, the R in gained formula (1) the polyamic acid precursor so
xBut just be described sensitization polymeric group.If R
xBut be the sensitization polymer-based group, gained amic acid esters oligomer can produce molecule and intermolecular chemical bond and forms crosslinked (crosslinking) in follow-up synthesis of polyimides resin process.
The present invention provides a kind of precursor composition that is used to prepare polyimide in addition, and it comprises the amic acid esters oligomer and the solvent of aforementioned formula (1).
In the present composition, employed preferred solvents is a tool polar non-protonic solvent.Say it (but not as limit) for example, the following group that is formed of the optional freedom of described non-protonic solvent: N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), toluene (toluene), dimethylbenzene (xylene) and its mixture.
In precursor composition of the present invention, in the gross weight of integrally combined thing, the content of described amic acid esters oligomer is 15% to 70%, is preferably 30% to 60%; The content of described solvent is 20% to 80%, is preferably 45% to 75%.
The present composition can optionally comprise those skilled in the art's known additives, for example light trigger, silane coupling agent, leveling agent, tranquilizer, catalyzer and/or defoamer etc.
When aforementioned formula (1) but amic acid esters oligomer when having sensitization polymeric group, can optionally add light trigger.Be applicable to that light trigger of the present invention there is no particular restriction, it can be selected from the following group that forms: benzophenone (benzophenone), bitter almond oil camphor (benzoin), 2-hydroxy-2-methyl-1-Propiophenone (2-hydroxy-2-methyl-1-phenyl-propan-1-one), 2,2-dimethoxy-1,2-phenylbenzene second-1-ketone (2,2-dimethoxy-1,2-diphenylethan-1-one), 1-hydroxycyclohexylphenylketone (1-hydroxy cyclohexylphenyl ketone), 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (2,4,6-trimethylbenzoyl diphenylphosphine oxide), N-phenylglycine, 9-phenylacridine (9-phenylacridine), benzyl dimethyl ketal (benzyldimethylketal), 4,4 '-two (diethylamide) benzophenone, 2,4,5-triarylimidazoles dipolymer (2,4,5-triarylimidazole dimers) and its mixture; Preferable light trigger is a benzophenone.Particularly, in the gross weight of precursor composition of the present invention, the content of used light trigger is 0.01 to 20 weight %, is preferably 0.1 to 5 weight %.
Silane coupling agent commonly used is selected from (but being not limited to) by the following group that forms: 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl three ethoxy alkyl silanes and its mixture.
The present invention also provides a kind of polyimide, and it is that polyamic acid precursor polymerization by aforementioned formula (1) gets.Say it (but not as limit) for example, polyimide of the present invention can make by polymerization process shown in the following schema:
The synthetic method of tradition polyimide needs the polyamic acid of first synthetic macromolecule amount to be used as precursor, but because molecular weight is too high, viscosity is too big, so that the operability variation, is easy to produce shortcomings such as levelling property is bad when coating.In addition, too high polyamic acid molecular weight can the shortening because of intermolecular interaction and molecular chain bond distance produce very big internal stress when the precursor imidization, cause institute's substrates coated film buckling deformation.In addition, in conventional polyimide synthetic method, the solid content when its polyreaction forms polyamic acid is approximately between 10% to 30%, so volumetric shrinkage is bigger than (shrinkage ratio) after cyclisation, need repeatedly coating can reach the thickness of product requirement, increase the processed complex degree.
Amic acid esters oligomer of the present invention, it is characterized by and have ester group simultaneously (end group of C (O) OR and carboxyl (C (O) OH) is in the steady state (meta-stable status) that is situated between, therefore at room temperature can't with the amino (H of self
2N) produce reaction, but because polyamic acid precursor molecules amount is low, therefore handling good, coating can reach smooth effect.After solidifying (post cure), be warmed up to more than 100 ℃, amino can be reduced into acid anhydrides with ester group and carboxyl end groups earlier, and then be reacted into the amic acid esters oligomer, the gained oligomer further aggregates into bigger molecule afterwards, and then condensation provides the polyimide of tool excellent heat character, mechanical properties and tensile property.Compare the bigger polyphosphazene polymer amido acid of the employed viscosity of routine techniques, the present invention uses the less amic acid esters oligomer of viscosity as precursor, so when coating, can present than high-leveling and operability.
Another feature of polyimide of the present invention is, because employed precursor composition is when carrying out imidization, contained amic acid esters oligomer carries out intramolecular cyelization earlier, carries out intermolecular polymerization and cyclic action again, can effectively reduce the remaining internal stress of polyimide.Compare with routine techniques, the polyimide that gets by the cyclisation of precursor composition of the present invention institute has the not advantage of warpage.
Polyimide of the present invention, because its precursor composition has highly filled (high solids content), contain less solvent, so can shorten the soft roasting time and reduce soft roasting temperature, reduce the volumetric shrinkage phenomenon that is caused because of a large amount of solvent evaporates, and have drying and forming-film speed and reach the required advantages such as gluing number of times of product requirement thickness with being reduced to soon.
On the other hand, prepared in the past the required cyclisation temperature of polyimide usually up to 300 ℃ to 350 ℃, yet precursor composition of the present invention can carry out cyclization under about 200 ℃ to 250 ℃ temperature, more can reduce running cost.
In addition, at general fashionable some monomers or the short chain oligomer of all can adding of polyphosphazene polymer, make molecule and intermolecular energy form crosslinked (Crosslinking), yet, but precursor of the present invention is because of containing the sensitization polymer-based group, but and then when solidifying self-crosslinking, so precursor composition of the present invention can need not to comprise extra unsaturated monomer or oligomer, significantly reduces processed complex degree and tooling cost.
Following example will be used for exemplifying enforcement of the present invention aspect, and explain technical characterictic of the present invention, be not to be used for limiting protection category of the present invention.Any those skilled in the art can unlabored change or the arrangement of the isotropism scope that all belongs to the present invention and advocated, and the scope of the present invention should be as the criterion with appended claim scope.
Example
Following examples 1 to 20 prepare the making step and the condition of the composition that the present invention is used to form polyimide for illustration, and 1 of comparative example is about the prepared composition that is used to form polyimide of routine techniques.
Embodiment 1
The pyromellitic acid dianhydride (pyromellitic dianhydride, hereinafter referred is PMDA) of 21.81 grams (0.1 mole) is dissolved in the N-Methyl pyrrolidone (N-methyl-2-pyrrolidone of 200 grams; Hereinafter referred is NMP) in, heating gained mixture to 50 ℃ and reaction were stirred two hours.Slowly splash into the vinylformic acid 2-hydroxy methacrylate (2-hydroxyethyl acrylate, hereinafter referred is HEA) of 1.161 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.Thereafter, with 4,4 of 20.024 grams (0.1 mole) '-oxydianiline (4,4 '-oxydianiline, hereinafter referred is ODA) be added in the solution, after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Comparative example 1
The ODA of 20.024 grams (0.1 mole) is dissolved among the NMP of 200 grams, ice bath reaches 0 ℃ and reaction and stirred one hour, thereafter the anhydride phthalic acid (phthalic anhydride) that adds 0.29 gram (0.002 mole), question response stirred after one hour, the PMDA that slowly adds 21.59 grams (0.099 mole) again, reaction was stirred 12 hours under 50 ℃ fixed temperature.
Embodiment 2
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the 2-hydroxyethyl methacrylate (2-hydroxyethylmethacrylate of 13.01 grams (0.01 mole); Hereinafter referred is HEMA), reaction was stirred two hours under 50 ℃ fixed temperature.ODA with 20.024 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 3
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 1.161 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.Ursol D (para-phenylenediamine, hereinafter referred is pPDA) with 10.814 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 4
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 13.01 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.PPDA with 10.814 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 5
The PMDA of 21.81 grams (0.1 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reacts stirring two hours down.Slowly splash into the HEA of 1.161 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.Dimethyl benzidine between 21.23 grams (0.1 mole) (2,2-dimethyl-4,4-diamino-biphenyl, hereinafter referred is DMDB) is added in the solution, after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature more again.
Embodiment 6
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 13.01 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.DMDB with 21.23 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 7
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 1.161 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.Again with 21.23 the gram (0.1 mole) adjacent dimethyl benzidine (o-Tolidine; Hereinafter referred is oTLD) be added in the solution, after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 8
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 13.01 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.OTLD with 21.23 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 9
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 1.161 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.Again with two (trifluoromethyl) benzidine (2 between 32.02 grams (0.1 mole), 2 '-bis (trifluoromethyl) benzidine, hereinafter referred is TFMB) be added in the solution, after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 10
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 13.01 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.TFMB with 32.02 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 11
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the methyl alcohol of 0.32 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.ODA with 20.024 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 12
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the Virahol of 0.601 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.ODA with 20.024 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 13
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the methyl alcohol of 0.32 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.PPDA with 10.814 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 14
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the Virahol of 0.601 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.PPDA with 10.814 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 15
The PMDA of 21.81 grams (0.1 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reacts stirring two hours down.Slowly splash into the methyl alcohol of 10.32 grams (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.DMDB with 21.23 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 16
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the Virahol of 0.601 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.DMDB with 21.23 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 17
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the methyl alcohol of 0.32 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.OTLD with 21.23 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 18
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the Virahol of 0.601 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.OTLD with 21.23 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 19
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the methyl alcohol of 0.32 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.TFMB with 32.02 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
Embodiment 20
The PMDA of 21.81 grams (0.1 mole) are dissolved among the NMP of 200 grams, are heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the Virahol of 0.601 gram (0.01 mole), reaction was stirred two hours under 50 ℃ fixed temperature.TFMB with 32.02 grams (0.1 mole) is added in the solution again, and after treating to dissolve fully, reaction was stirred six hours under 50 ℃ fixed temperature again.
The test of polyimide physical property
At first utilize the molecular weight related data of the HT-GPC apparatus measures gained polyamic acid of Waters Model:2010, as shown in table 1 below:
Table 1
| Test product | M n | M w | MP (1) | PD (2) |
| The present invention (embodiment 1) | 16,129 | 23,530 | 21,238 | 1.458866 |
| Routine techniques (comparative example 1) | 106,828 | 263,324 | 266,462 | 2.464926 |
(1)Peak molecular weight
(2)Polymer dispersed (polydispersity)
By table 1 data as can be known, the inventive method can provide the polyamic acid of tool than the low-grade polymer dispersiveness, and just the molecular weight ranges narrow distribution of obtained polyamic acid, height molecular weight differences be apart from less, its better quality.
Get embodiment 1 and make film in the mode of rotary coating with comparative example 1 resulting composition.Further toast with baking oven, and heating curve is divided into three sections, is respectively 150 ℃/60min, 250 ℃/60min and 350 ℃/120min, its heat-up rate are 2 ℃/min again, and afterwards, cooling is risen again.Carry out the physical property test.
Then, utilize omnipotent puller system (the hot bending determinator Model 9102 that HTC produces) to carry out the test of polyimide film mechanical properties.The gained polyimide film is cut into the size of 12cm * 10cm * 0.25mm, mount on described omnipotent puller system, under 23 ℃ of temperature, carry out, speed setting is 10mm/min, respectively to making tensile test by embodiment 1 composition and comparative example 1 composition gained polyimide film, to measure different tensile strength, the result is as shown in table 2:
Table 2
| Test product | Draw anti-intensity (MPa) | Extended length per-cent (%) |
| The present invention (embodiment 1) | 78.896 | 11.185％ |
| Routine techniques (comparative example 1) | 74.3 | 5.415％ |
Show that by table 2 result polyimide film provided by the present invention can represent comparatively excellent tensile strength and elongation.
Claims (14)
1. the precursor of a polyimide, the structure of its tool following formula (1):
Wherein
R is that the straight or branched alkyl of 1 to 14 carbon atom of tool, the aryl or aralkyl or the ethene of 6 to 14 carbon atoms of tool are unsaturated group;
R
xIndependent separately is that H or ethene are unsaturated group;
G independently is 4 valency organic groups separately;
P independently is the divalent organic group separately; And
M is 0 to 100 integer.
2. precursor according to claim 1, wherein said ethene are that unsaturated group is selected from following group: vinyl, propenyl, methylpropenyl, n-butene base, isobutenyl, ethenylphenyl, propenyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group, metacryloxy hexyl, and the group of tool following formula (2)
R wherein
1For stretching phenyl, C
3-C
8Stretch the C of cycloalkyl, straight or branched
1-C
8Stretch alkyl, C
1-C
8Stretch thiazolinyl or C
1-C
8Hydroxyl is stretched alkyl, and R
2Be hydrogen or C
1-C
4Alkyl.
3. precursor according to claim 1, wherein R
xIndependent separately is H, methacrylic acid-2-hydroxy propyl ester base, Jia Jibingxisuanyizhi base, ethyl propenoate base, propenyl, methylpropenyl, n-butene base or isobutenyl.
4. precursor according to claim 1, wherein R
xIndependent separately is H or methacrylic acid-2-hydroxy propyl ester base.
5. precursor according to claim 1, wherein said 4 valency organic groups are selected from the group that is made of following groups:
Wherein Y independently is hydrogen, halogen, C separately
1-C
4Perfluoroalkyl or C
1-C
4Alkyl, and B is-CH
2-,-O-,-S-,-CO-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-.
6. precursor according to claim 5, wherein said 4 valency organic groups are selected from the group that is made of following groups:
7. precursor according to claim 1, wherein said divalent organic group is selected from the group that is made of following groups:
Wherein X independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; A is-O-,-S-,-CO-,-CH
2-,-OC (O)-or-CONH-; And respectively do for oneself 1 to 3 integer of w and z.
8. precursor according to claim 7, wherein said divalent organic group is selected from the group that is made of following groups:
9. precursor according to claim 1, wherein m is 5 to 25 integer.
10. precursor according to claim 1, wherein R is selected from the group that is made of following groups:
Wherein n is 0 to 10 integer.
11. the precursor composition of a polyimide, it comprises precursor according to claim 1 and solvent.
12. composition according to claim 11, wherein said solvent is selected from the group that is made up of N-N-methyl 2-pyrrolidone N-, N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene and its mixture.
13. composition according to claim 11; it further comprises light trigger; described light trigger is selected from by benzophenone, bitter almond oil camphor, 2-hydroxy-2-methyl-1-Propiophenone, 2; 2-dimethoxy-1; 2-phenylbenzene second-1-ketone, 1-hydroxycyclohexylphenylketone, 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, N-phenylglycine, 9-phenylacridine, benzyl dimethyl ketal, 4; 4 '-two (diethylamide) benzophenone, 2; 4, the group that 5-triarylimidazoles dipolymer and its mixture are formed.
14. a polyimide, it is to obtain by polymerization precursor according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102363710A (en) * | 2011-08-03 | 2012-02-29 | 东华大学 | Lacquer for high-temperature resistant polyimide enameled wire, preparation and application thereof |
| CN102604093A (en) * | 2012-03-26 | 2012-07-25 | 长春高琦聚酰亚胺材料有限公司 | Preparation method of polyimide |
| DE102012102131A1 (en) | 2011-03-18 | 2013-04-11 | Eternal Chemical Co., Ltd. | Method for producing a flexible component |
| DE102016210892A1 (en) | 2015-06-17 | 2016-12-22 | Eternal Materials Co., Ltd. | A metal-clad laminate, manufacturing method thereof, and a method of manufacturing a flexible printed circuit board using the same |
| CN108690196A (en) * | 2017-03-31 | 2018-10-23 | 长兴材料工业股份有限公司 | Polyimide precursor composition, use thereof, and polyimide prepared therefrom |
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2007
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|---|---|---|---|---|
| DE102012102131A1 (en) | 2011-03-18 | 2013-04-11 | Eternal Chemical Co., Ltd. | Method for producing a flexible component |
| CN102363710A (en) * | 2011-08-03 | 2012-02-29 | 东华大学 | Lacquer for high-temperature resistant polyimide enameled wire, preparation and application thereof |
| CN102604093A (en) * | 2012-03-26 | 2012-07-25 | 长春高琦聚酰亚胺材料有限公司 | Preparation method of polyimide |
| US10414868B2 (en) | 2012-03-26 | 2019-09-17 | Changchun Hipolyking Co., Ltd. | Preparation method of polyimide |
| DE102016210892A1 (en) | 2015-06-17 | 2016-12-22 | Eternal Materials Co., Ltd. | A metal-clad laminate, manufacturing method thereof, and a method of manufacturing a flexible printed circuit board using the same |
| US10765008B2 (en) | 2015-06-17 | 2020-09-01 | Eternal Materials Co., Ltd. | Metal clad laminate, preparation method thereof, and method for preparing flexible circuit board by using the same |
| CN108690196A (en) * | 2017-03-31 | 2018-10-23 | 长兴材料工业股份有限公司 | Polyimide precursor composition, use thereof, and polyimide prepared therefrom |
| US11034797B2 (en) | 2017-03-31 | 2021-06-15 | Eternal Materials Co., Ltd. | Polyimide precursor composition, use thereof and polyimide made therefrom |
| CN108690196B (en) * | 2017-03-31 | 2021-09-03 | 长兴材料工业股份有限公司 | Polyimide precursor composition, use thereof, and polyimide prepared therefrom |
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| CN101117384B (en) | 2011-04-13 |
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