CN101048442A - Poly(imide/azomethine) copolymer, poly(amic acid/azomethine) copolymer and positive type photosensitive resin compositions - Google Patents
Poly(imide/azomethine) copolymer, poly(amic acid/azomethine) copolymer and positive type photosensitive resin compositions Download PDFInfo
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- CN101048442A CN101048442A CNA2005800373468A CN200580037346A CN101048442A CN 101048442 A CN101048442 A CN 101048442A CN A2005800373468 A CNA2005800373468 A CN A2005800373468A CN 200580037346 A CN200580037346 A CN 200580037346A CN 101048442 A CN101048442 A CN 101048442A
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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Abstract
The invention provides a poly(imide/azomethine) copolymer having a low coefficient of linear thermal expansion and its manufacture method; a process for the production of the same; a poly(amic acid/azomethine) copolymer which is a precursor of the above copolymer; positive type photosensitive compositions comprising the poly(amic acid/azomethine) copolymer and photosensitizers; and a process for forming fine patterns from the compositions. The poly(imide/azomethine) copolymer is composed of azomethine repeating units represented by the general formula (1) and imide repeating units represented by the general formula (2), while the poly(amic acid/azomethine) copolymer serving as the main component of the photosensitive compositions is composed of azomethine repeating units represented by the general formula (1) and amic acid repeating units represented by the general formula (3): wherein A and D are each a divalent aromatic or aliphatic group; and B is a tetravalent aromatic or aliphatic group.
Description
Technical field
The fine pattern manufacture method that the present invention relates to have concurrently useful poly-(imide-azomethine) multipolymer of lower thermal expansivity, high glass transition and excellent toughness and manufacture method thereof, promptly poly-(amido acid-azomethine) multipolymer of its precursor polymer, contains the positive type photosensitive organic compound of precursor polymer and sensitizer, gathered the fine pattern of (imide-azomethine) multipolymer by said composition.
Background technology
As to the flexible printed wiring circuit with substrate, belt bonding automatically (テ one プ オ one ト メ one シ ヨ Application ボ Application デ イ Application グ) with one of key property of various used for electronic device insulating material such as the protective membrane of base material, semiconductor element, unicircuit interlayer insulating film, can heat-stable thermotolerance in the time of can enumerating soldering.At present, as the used for electronic device heat-resistant insulation material that adapts to such requirement, what be widely known by the people is polyimide.
Yet, variation along with the insulating material purposes, for insulating material, except that thermotolerance, also require low-k, low heat expansion property, high transparent, high frequency characteristic (low dielectric loss tangent), low water absorbable, high-dimensional stability, binding property, processibility etc., but the polyimide that uses as the used for electronic device insulating material usually at present not necessarily fully satisfies such characteristic that requires.Thus, carrying out carrying out the development research of the compound polyimide etc. of molecular modification energetically with the thermotolerance polymer beyond the polyimide, with other polymer and compoundization of polymeric amide.
Usually, the thermotolerance that polyimide is high is rotated based on stiff backbone skeleton and bound intramolecularly, as the thermotolerance polymer beyond the polyimide with same rigid backbone, the poly methylene imine that can expect to make by the polycondensation of dialdehyde and diamines is as new heat-resistant insulation material.
Therefore but poly methylene imine precipitates in polymerization system with the low polymerization degree state in the starting stage of polycondensation because of its rigid structure, has the shortcoming (referring to non-patent literature 1) of the poly methylene imine that is difficult to obtain high-polymerization degree.When the polymerization degree of poly methylene imine was hanged down, mutual winding did not take place in polymer chain each other, loses toughness, and the result cracks on its cast film.Therefore, present situation is: the example of report that does not almost have the membrane property of relevant poly methylene imine.
Technology as the polymerization degree that improves poly methylene imine, proposed by in the synthesis material of poly methylene imine, using a part of fluoromonomers or the high monomer of bendability, make power reduction between polymer molecule, improve the solubleness (referring to non-patent literature 2, patent documentation 1, patent documentation 2) of poly methylene imine in polymerization system.By these technology, can expect to suppress poly methylene imine and precipitate in the polymerization starting stage.
In addition, in recent years, the low-thermal-expansionization of high temperature insulation film has become important problem owing to reason as described below.In general common solvent, being example for insoluble polyimide, the polyimide precursor of solubility is dissolved in the amides organic solvent, it is coated on the metal substrate and drying after, by under 250 ℃～350 ℃, carrying out thermal dehydration ring-closure reaction (imidization reaction), form polyimide film.Therefore, polyimide/metal substrate multilayer body is being cooled to the process of room temperature from the imidization temperature, is producing thermal stresses, this thermal stresses often causes serious problems such as warpage, film are peeled off, crackle.Recently,, begin to adopt multi-layer wire substrate along with the densification of electronic circuit, even but being unlikely to produce the peeling off of film, crackle, the stress-retained reliability of device that also makes of multilager base plate significantly reduces.In addition, in the imidization operation, the thermal linear expansion coefficient difference between metal substrate and the polyimide film is big more, and perhaps acyl Asiaization temperature is high more, and the stress of generation will increase thereupon.Therefore, the low-thermal-expansionization of high temperature insulation film has become the problem of the task of top priority.
For example, about the low-thermal-expansionization of polyimide, the thermal linear expansion coefficient of common polyimide is in the scope of 50～90ppm/K, and for example the thermal linear expansion coefficient 17ppm/K of copper is much bigger than metal substrate.Therefore, carried out making the thermal expansivity of polyimide to be similar to the numerical value of the thermal linear expansion coefficient of copper, for example research below about 20ppm/K (referring to non-patent literature 3), in this research, the general prerequisite of the low-thermal-expansionization of report polyimide is: backbone structure is linear, and inner rotation is in bond, is rigidity.
At present, as the low heat expansion property polyimide material of practicality, behaving most is well known that by 3, the polyimide that 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and Ursol D form.Though knownly also depend on thickness or create conditions that this polyimide film demonstrates the low-down thermal linear expansion coefficient (referring to non-patent literature 4) of 5～10ppm/K.
More known other polyimide that demonstrates low thermal expansion characteristics, these polyimides have bar none linear, inflexible main chain backbone, for example the polyimide of following combination demonstrates low thermal coefficient of expansion: as the tetracarboxylic dianhydride, remove 3,3 ', 4, outside 4 '-biphenyl tetracarboxylic dianhydride, also has pyromellitic dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride; As diamines, except that Ursol D, also have 2,2 '-two (trifluoromethyl) p-diaminodiphenyl, anti--1,4-cyclohexane diamine, ortho-tolidine ,-tolidine etc.
Manifesting of the low thermal coefficient of expansion of these polyimide films is based on the interior orientation of spontaneous face that imidization causes.That is to say, orientation degree in the stage face of polyimide precursor curtain coating on substrate is low, but during hot-imide, orientation degree sharply increases (referring to non-patent literature 4) in the face.
For the poly methylene imine class, in order to manifest low thermal expansion characteristics, rectilinearity and inflexible main chain backbone also are indispensable.But, during with terephthalaldehyde and Ursol D combination, as mentioned above, produce precipitation at the polymerization initial stage, be difficult to obtain high polymers.
By in meta-cresol, making i.e. 2,2 '-two (trifluoromethyl) benzidine reaction of rigidity fluoro diamines of terephthalaldehyde and formula (d) expression, can obtain to have the high polymers (referring to non-patent literature 5) of the poly methylene imine of rigid backbone.But serious gonorrhoea takes place because of forming liquid crystal in its cast film, and extremely fragile.
[Chemical formula 1]
In the rectilinearity of significantly not damaging main chain and inflexible scope, for example by copolymerization on a small quantity suc as formula the bendability diamines of (e) or formula (f) expression, the toughness of poly methylene imine cast film significantly increases (referring to non-patent literature 5).
[Chemical formula 2]
But, by 2 of formula (d), under the situation of the rigidity poly methylene imine co-polymer membrane that 2 '-two (trifluoromethyl) p-diaminodiphenyl obtains as the main component and the terephthalaldehyde of diamines, its thermal linear expansion coefficient height is 90ppm/K, can not obtain required low thermal expansion characteristics (referring to non-patent literature 5).This statement of facts, even main chain backbone is rectilinearity and inflexible, only evaporating solvent in the solution casting process is also insufficient as the factor of orientation degree in the face that causes height.
In recent years, shortening the research and development of the photosensitive polyimide (or its precursor polymer) of the fine pattern operation that forms polyimide film significantly carries out active, if but to have concurrently the unexistent characteristic of common polyimide for example the polyimide of low-k, low-thermal-expansion, high glass-transition temperature can further give photosensitivity, then can be provided in material exceedingly useful in the above-mentioned industrial field.
Recently, from the consideration to environment, compare with the minus that develops with organic solvent, the importance of the positive type photosensitive polyimide precursor that alkali develops improves constantly.Polyimide precursor (polyamic acid) was soluble originally in alkali, but by disperse the diazo naphthoquinone class sensitizer as dissolution inhibitor in polyamide acid film, becoming is insoluble to alkali.Secondly, if by the photomask irradiation ultraviolet radiation, then the diazo naphthoquinone class sensitizer of exposure portion has only exposure portion to dissolve in the alkaline aqueous solution because photoresponse is converted into alkaline bleach liquor soluble indene carboxylic acid, can form the eurymeric pattern on the principle.
But, because polyamic acid uses the solubleness in the tetramethylammonium hydroxide aqueous solution of alkaline-based developer too high general as the semi-conductor resist, so the additive effect deficiency of dissolution inhibitor, be difficult to form distinct pattern in many cases.For this reason, be necessary the structure of polyamic acid is implemented certain chemically modified, be controlled at the solvability in the alkaline aqueous solution.
As other importance except that the solubleness of control polyamic acid, can enumerate the transparency of polyamic acid.When the i of high pressure mercury vapour lamp ray (365nm) exposes down, the words that the transmissivity of the film of this wavelength is very not high, then irradiates light is by the crested of polyamic acid own, light is difficult to arrive sensitizer, therefore need time exposure, under extreme case, the photoresponse of sensitizer is subjected to overslaugh, can not form pattern.
As mentioned above, contain 3,3 ', 4, though the polyimide film of 4 '-biphenyl tetracarboxylic dianhydride and Ursol D is widely known by the people as the low-thermal-expansion polyimide, be 0% as the polyamide acid film of its precursor in fact to the transmissivity of i ray, be difficult to form light pattern.This is because irradiates light is covered by polyamic acid itself.
On the other hand, contain 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and anti--1, the polyamide acid film of 4-cyclohexane diamine demonstrates extremely high i radiant transmittance (referring to patent documentation 3), and the polyimide film that its curing obtains is demonstrated as low-thermal-expansion, low-k, the good rerum natura (referring to non-patent literature 6, non-patent literature 7) of high glass-transition temperature balance.But, too high even under the situation of this polyimide precursor because of its solubleness in alkaline aqueous solution, also be difficult to form light pattern, thereby need practicably form light pattern with it.
Therefore, even also expectation can expect that good stable on heating poly methylene imine class when demonstrating the rerum natura good as low-thermal-expansion, low-k, high glass-transition temperature balance, also can practicably form light pattern.
Non-patent literature 1: organic chemistry is synthetic, the 41st volume, and nineteen eighty-three, p.972-984
Non-patent literature 2: Polymer Chemistry and Physics (Macromolecular Chemistryand Physics), the 195th volume, 1994, p.1877-1889
Non-patent literature 3: polymkeric substance (Polymer), the 28th volume, 1987, p.2282-2288
Non-patent literature 4: polymer (Macromolecules), the 29th volume, 1996, p.7897-7909
Non-patent literature 5: the pre-original text collection of polymer association, the 52nd volume, 1996, No. 6, p.1295
Non-patent literature 6: high-performance polymer (High Performance Polymers), the 13rd volume, calendar year 2001, p.S93-S106
Non-patent literature 7: high-performance polymer (High Performance Polymers), the 15th volume, 2003, p.47-64
Patent documentation 1: the spy opens clear 64-79233 communique
Patent documentation 2: the spy opens flat 2-42372 communique
Patent documentation 3: the spy opens the 2002-161136 communique
Summary of the invention
The object of the present invention is to provide poly-(imide-azomethine) multipolymer with low coefficient of linear thermal expansion and manufacture method thereof, as poly-(amido acid-azomethine) multipolymer of its precursor, contain the positive type photosensitive organic compound of this multipolymer and sensitizer and by the method for the fine pattern of poly-(imide-azomethine) multipolymer of this positive type photosensitive organic compound manufacturing.
The inventor finds can achieve the above object, thereby finish the present invention by being that the amido acid residue is introduced in the poly methylene imine with the intramolecular cyclization reaction position.
That is, the invention provides poly-(imide-azomethine) multipolymer of the imide polymerized unit of the azomethine polymerized unit that comprises formula (1) and formula (2).
[chemical formula 3]
(in formula (1) and formula (2), A and D are respectively the aromatic group or the aliphatic group of divalence, and B represents quaternary aromatic group or aliphatic group.)
The present invention also provides the manufacture method that obtains above-mentioned poly-(imide-azomethine) multipolymer, wherein the diamines of formula (a), the acid dianhydride of formula (b) and the dialdehyde of formula (c) are mixed, and polymerization, formation comprises poly-(amido acid-azomethine) multipolymer of the amido acid polymerized unit of the azomethine polymer unit of formula (1) and formula (3), and poly-(amido acid-azomethine) multipolymer of gained is carried out imidization handle.
[chemical formula 4]
H
2N-A-NH
2 (a)
OHC-D-CHO (c)
(in formula (a), formula (b) and formula (c), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group.)
[chemical formula 5]
(in formula (1) and formula (3), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group.)
The present invention also provides poly-(amido acid-azomethine) multipolymer, and it is the precursor polymer of above-mentioned poly-(imide-azomethine) multipolymer, comprises the azomethine polymerized unit of formula (1) and the amido acid polymerized unit of formula (3).
[chemical formula 6]
(in formula (1) and formula (3), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group.)
The present invention also provides the positive type photosensitive organic compound that contains above-mentioned poly-(amido acid-azomethine) and diazo naphthoquinone class sensitizer.
The present invention further provides the manufacture method of fine pattern, it is with above-mentioned positive type photosensitive organic compound system film, gained positive type photosensitive organic compound film is carried out after pattern exposure handles, carry out the alkali development treatment, further carry out the polyimide processing, gathered the fine pattern of (imide-azomethine) multipolymer.
Poly-(imide-azomethine) multipolymer of the present invention is by obtaining as promptly poly-(amido acid-azomethine) multipolymer imidization of polyimide precursor of having introduced the amido acid residue at intramolecularly at intramolecular cyclization reaction position.Therefore, poly-(imide-azomethine) multipolymer of the present invention becomes the polymkeric substance of low-thermal-expansionization.In addition, the resin combination that constitutes by poly-(amido acid-azomethine) multipolymer and sensitizer demonstrate can pattern exposure photosensitivity, and become the positive type photosensitive organic compound that can alkali develops.Utilize this positive type photosensitive organic compound, can obtain having lower specific inductivity, the fine pattern of poly-(imide-azomethine) multipolymer of lower thermal expansivity, high glass transition.
Description of drawings
Fig. 1 is the IR collection of illustrative plates of poly-(amido acid-azomethine) polymkeric substance of experiment 1a.
Fig. 2 is the IR collection of illustrative plates that gathers (imide-azomethine) polymkeric substance that (amido acid-azomethine) polymkeric substance imidization obtains that gathers with experiment 1a.
Embodiment
Explain the present invention below.
Poly-(imide-azomethine) multipolymer of the present invention comprises the azomethine polymerized unit of above-mentioned formula (1) and the imide polymerized unit of formula (2).This multipolymer not only demonstrates good thermotolerance, and demonstrate low-thermal-expansion, low-k, the good rerum natura of high glass-transition temperature balance more than 250 ℃ that is lower than 30ppm/K, and in the molecule before imidization owing to there is an amido acid residue, therefore diazo naphthoquinone class sensitizer is engaged in the precursor before the imidization, become positive type photosensitive organic compound, therefore can form light pattern.
Constitute the molar fraction of the imide polymerized unit of the azomethine polymerized unit of formula (1) of poly-(imide-azomethine) multipolymer of the present invention and formula (2), when a side is more very few than the opposing party, when for example the imide residue is very few, can not get low thermal expansion characteristics, when if the azomethine residue is very few in addition, then the eurymeric light pattern might can not be formed, therefore, if the molar fraction of formula (1) is X, the molar fraction of formula (2) is during as 1-X, and X is preferably 0.05～0.95, more preferably 0.1～0.9 scope.
As mentioned above, substituent A and substituent group D in the imide polymerized unit of the azomethine polymerized unit of formula (1) and formula (2) are represented divalent aromatic base or aliphatic group respectively, and substituent B is represented quaternary aromatic group or aliphatic group.
Wherein, the divalent aromatic base of substituent A or aliphatic group are the residues from the fluorinated diamine class, and two amino can enumerating particularly described fluorinated diamine class remove the residue that obtains.As particularly preferred substituent A, can enumerate from the fluorinated diamine class is the residue of 2,2 ' of above-mentioned formula (d)-two (trifluoromethyl) p-diaminodiphenyl.Also can with from the residue of the bendability fluorinated diamine of above-mentioned formula (e) or formula (f) with from the residue of the diamines of above-mentioned formula (d) and use.At this moment, too high from the ratio of the residue of the fluorinated diamine of formula (e) or formula (f), therefore the tendency that then has the thermal linear expansion coefficient of poly-(imide-azomethine) multipolymer to enlarge markedly should be noted that.At this moment, the exist ratio of the diamines of formula (d) in total diamines is at least 50mol%.
In addition, divalent aromatic base or aliphatic group as substituent A, except that residue from above-mentioned fluorinated diamine class, in the scope that requires characteristic of the polymerisation reactivity that does not significantly damage poly-(amido acid-azomethine) multipolymer or poly-(imide-azomethine) co-polymer membrane, can also enumerate from the aromatic diamine shown below or the residue of aliphatic diamine.
Residue as substituent A from aromatic diamine, can enumerate residue: p-phenylenediamine from following compound, between-phenylenediamine, 2, the 4-diaminotoluene, 2, the 5-diaminotoluene, 2,4-diamino dimethylbenzene, 2,4-diamino デ ユ レ Application, 4,4 '-diaminodiphenyl-methane, 4,4 '-methylene-bis (2-aminotoluene), 4,4 '-methylene-bis (2-ethylaniline), 4,4 '-methylene-bis (2, the 6-xylidine), 4,4 '-methylene-bis (2, the 6-Diethyl Aniline), 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 2,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 4,4 '-diaminobenzene formylaniline, p-diaminodiphenyl, 3,3 '-dihydroxybiphenyl amine, 3,3 '-dimethoxy benzidine, ortho-tolidine, between-tolidine, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, two (4-(3-amino-benzene oxygen) phenyl) sulfone, two (4-(4-amino-benzene oxygen) phenyl) sulfone, 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-aminophenyl) propane of 2-, right-triphenyldiamine etc.Can also using more than 2 kinds with these residues.
Residue as substituent A from aliphatic diamine, can enumerate residue: anti-form-1 from following compound, the 4-diamino-cyclohexane, cis-1, the 4-diamino-cyclohexane, 1,4-diamino-cyclohexane (trans/cis mixture), 1, the 3-diamino-cyclohexane, isophorone diamine, 1,4-hexanaphthene two (methylamine), 2,5-two (amino methyl) two ring [2.2.1] heptane, 2,6-two (amino methyl) two ring [2.2.1] heptane, 3,8-two (amino methyl) three ring [5.2.1.0] decane, 1,3-diamino diamantane, 4,4 '-methylene-bis (cyclo-hexylamine), 4,4 '-methylene-bis (2-methylcyclohexyl amine), 4,4 '-methylene-bis (2-ethyl cyclo-hexylamine), 4,4 '-methylene-bis (2, the 6-dimethylcyclohexylam,ne), 4,4 '-methylene-bis (2,6-diethyl cyclo-hexylamine), 2, two (4-aminocyclohexyl) propane of 2-, 2, two (4-aminocyclohexyl) HFC-236fa of 2-, 1, the 3-propylene diamine, 1, the 4-tetramethylene-diamine, 1, the 5-five methylene diamine, 1, the 6-hexamethylene-diamine, 1,7-heptamethylene diamines, 1,8-eight methylene diamine, 1,9-nine methylene diamine etc.Also can also using more than 2 kinds with these residues.
In addition, the tetravalence aromatic group of substituent B or aliphatic group are the residues from the tetracarboxylic dianhydride, specifically four carboxyls of this tetracarboxylic dianhydride are removed and the residue that obtains.As particularly preferred substituent B, consider from giving poly-(imide-azomethine) multipolymer low coefficient of linear thermal expansion, high glass-transition temperature and enough toughness aspects, can enumerate from pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride's residue.Can and use these residues.
In addition, tetravalence aromatic group or aliphatic group as substituent B, except that above-mentioned residue from the tetracarboxylic dianhydride, in the scope that requires characteristic of the polymerisation reactivity that does not significantly damage poly-(amido acid-azomethine) multipolymer or poly-(imide-azomethine) co-polymer membrane, also can enumerate residue from acid dianhydride shown below.
As the quadribasic acid dianhydride of substituent B, can enumerate 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, 2,2 '-two (3,4-dicarboxyl phenyl) hexafluoro propionic acid dianhydride, 2,2 '-two (3,4-dicarboxyl phenyl) propionic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride etc.As copolymer composition, these acid dianhydrides can use separately, perhaps also can use more than 2 kinds.
The divalent aromatic base of substituent group D or aliphatic group are the residues from dialdehyde.The residue that specifically two aldehyde radicals of above-mentioned dialdehyde is removed and obtain.As particularly preferred substituent group D, be residue from terephthalaldehyde.
In addition, as the divalent aromatic base of substituent group D, except above-mentioned residue from terephthalaldehyde, not significantly the infringement require in the scope of characteristic, also can and use residue from other dialdehyde.There is no particular limitation, can enumerate from isophthalic aldehyde, 44 '-phenyl ether dialdehyde, 4,4 '-ditan dialdehyde, 4,4 '-sulfobenzide dialdehyde, 1,5-naphthalene dialdehyde, 2, the residue of 6-naphthalene dialdehyde etc.
In addition, as the divalent aliphatic base of substituent group D, can enumerate various residues from aliphatic dialdehyde.Wherein, in aliphatic dialdehyde, remove 1, outside straight or brancheds such as the 6-hexanedial aliphatic series dialdehyde, also comprise the ester ring type dialdehyde.As the divalent aliphatic base of preferred substituted D, can enumerate hexanaphthene-1,2-dialdehyde, hexanaphthene-1,3-dialdehyde, hexanaphthene-1,4-dialdehyde, cyclooctane-1,2-dialdehyde, cyclooctane-1,5-dialdehyde etc.
For the manufacturing of ester ring type dialdehyde, the aliphatic dihalide of selecting to have ring structure is as initial substance, and the halogenide of correspondence is converted into magnesium compound (Grignard reagent) or lithium compound, makes it then to get final product with suitable formylation initial substance effect.For example, as aliphatic dihalide, be cis/trans-1 selecting aliphatic six membered ring, during the 4-dibromo-cyclohexane, can pass through following path synthesizing cyclohexane 1 alkane 1,4-dialdehyde.In addition, can also the selected location isomer be cis/trans-1,2-dibromo-cyclohexane, cis/trans-1,3-dibromo-cyclohexane.In addition, also can use the aliphatic dihalide with ring structure of other annular atoms number.Using eight Yuans rings of aliphatic series is cis/trans-1, during 5-dibromo cyclooctane, and also can be synthetic by following path.Equally, can the selected location isomer be cis/trans-1 also, (reference: G.Boss and H.Gerlach, Chem.Ber., 1989,1199.) such as 2-dibromo cyclooctane.
[chemical formula 7]
Then, by comprising following operation (I) and manufacture method (II), can make poly-(imide-azomethine) multipolymer of the invention described above.
Operation (I)
At first, the acid dianhydride of the diamines of above-mentioned formula (a), formula (b) and the dialdehyde of formula (c) are mixed, and polymerization, form poly-(amido acid-azomethine) multipolymer of the amido acid polymerized unit of the azomethine polymerized unit that comprises formula (1) and formula (3).Wherein, substituent A, B and the D in formula (a), formula (b), formula (c) and the formula (3) is as explanation in formula (1) and formula (2).Therefore, the diamines of formula (a) is that the substituent A bonding in two amino and the above-mentioned formula (1) obtains, the acid dianhydride of formula (b) is the substituent B bonding of four carboxyls and above-mentioned formula (2), forms that acid anhydrides obtains, and the dialdehyde of formula (c) to be the substituent group D bonding of two aldehyde radicals and formula (1) obtain.
Particularly, with 2, the diamines of 2 '-two (trifluoromethyl) p-diaminodiphenyl equation (a) is dissolved in the N-N-methyl-2-2-pyrrolidone N-equal solvent, slowly adds the acid dianhydride of pyromellitic dianhydride equation (b) in the gained solution, at room temperature stir 30 minutes～a few hours, form clear solution.The dialdehyde that then slowly adds terephthalaldehyde powder equation (3) preferably stirred for several hour～a few days at room temperature, makes polymerization.Thus, obtain even and poly-(amido acid-azomethine) copolymer solution of heavy-gravity.Wherein, from the viewpoint of film toughness, the limiting viscosity of poly-(amido acid-azomethine) multipolymer is preferably 0.1dL/g above (condition determination: with ostwald's viscometer the N-N-methyl-2-2-pyrrolidone N-solution (0.5 weight %) of poly-(amido acid-azomethine) is measured at 30 ℃).
Be noted that and poly-(amido acid-azomethine) copolymer solution of gained directly can be put into down in the step operation (II), also can cooperate sensitizer to use as hereinafter described as positive type photosensitive organic compound.In addition,-cresols etc. is poisonous or when being difficult to that polymerization is gathered (amido acid-azomethine) multipolymer in the evaporable solvent, after also can suitably diluting polymeric solution, drip poor solvents such as methyl alcohol, ether, toluene, poly-(amido acid-azomethine) multipolymer is separated out with powder morphology, washing, after the drying, be dissolved in once more in the N-N-methyl-2-2-pyrrolidone N-etc., put in the aftermentioned operation (II).
In this operation, polymerization is carried out in charging as follows: the mole total amount of the dialdehyde of the acid dianhydride of formula (b) and formula (c) equals the mole total amount of the diamines of formula (a).Wherein, by regulating their mol ratio, if the molar fraction of the azomethine polymer unit of the formula (1) in poly-(amido acid-azomethine) multipolymer is X, when the molar fraction of establishing the amido acid polymerized unit of formula (3) is 1-X, X can be adjusted in 0.05～0.95 scope.
In addition, there is total addition level (monomer) concentration of dialdehyde of the acid dianhydride of diamines, formula (b) of (a) in the polymeric solution and formula (c) high more, the trend that the polymerization degree increases, but too high words, easily separate out polymer precipitation, therefore be generally 5～50 weight %, preferred 10～40 weight %.
As the preferred solvent that can in this operation, use, can preferably use the N-N-methyl-2-2-pyrrolidone N-,-cresols, N, N-N,N-DIMETHYLACETAMIDE etc., except that these, can also use N, N-diethyl acetamide, N, dinethylformamide, hexamethylphosphoramide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 1,3-dimethyl-2-imidazolone, 1,2-glycol dimethyl ether-two (2-methoxy ethyl) ether, tetrahydrofuran (THF), 1, non-protonic solvents such as 4-two alkane, picoline, pyridine, acetone, chloroform, toluene, dimethylbenzene; Phenol, neighbour-cresols, p-Cresol, neighbour-chlorophenol ,-chlorophenol, right-protic solvents such as chlorophenol.In addition, these solvents may be used alone, can also be 2 or more kinds in combination.
Operation (II)
Then, according to known imidization method, poly-(amido acid-azomethine) multipolymer of gained is carried out imidization handle.Can be gathered (imide-azomethine) multipolymer thus.
Particularly by the following method: the apparatus for coating of routines such as use rotary coating machine makes the organic solvent solution film forming of poly-(amido acid-azomethine) multipolymer, gained is gathered the film of (amido acid-azomethine) multipolymer in air, in the inert gas atmospheres such as nitrogen or in the vacuum, at 200 ℃～430 ℃, preferably under 250 ℃～400 ℃ temperature, heat-treat, perhaps, gathered the film of (imide-azomethine) multipolymer thus by preferably at room temperature flooding the method for 1 minute～a few hours carries out imidization in the acetic anhydride that contains basic catalysts such as pyridine or triethylamine.In the organic solvent solution of poly-(amido acid-azomethine) multipolymer, as required can the mixed oxidization stablizer, additives such as end closure agent, weighting agent, silane coupling agent, sensitizer, Photoepolymerizationinitiater initiater, sensitizing agent.
Then, the positive type photosensitive organic compound that uses poly-(amido acid-azomethine) multipolymer that obtains in operation (I) is described.
This positive type photosensitive organic compound contains poly-(amido acid-azomethine) multipolymer and the diazo naphthoquinone class sensitizer that obtains in operation (I).As polyimide precursor should poly-(amido acid-azomethine) multipolymer be soluble in alkali originally, but under the dispersed state of diazo naphthoquinone class sensitizer during film forming, diazo naphthoquinone class sensitizer plays dissolution inhibitor, and it is insoluble that film itself becomes alkali.On the other hand, if by photomask to this film irradiation ultraviolet radiation, then the diazo naphthoquinone class sensitizer in exposure portion is converted into the soluble indene carboxylic acid of alkali by photoresponse, therefore having only exposure portion is soluble in alkaline aqueous solution.Therefore can form the eurymeric pattern.
Object lesson as diazo naphthoquinone class sensitizer, can enumerate 1,2-naphthoquinones-2-two diazoes-5-sulfonic acid, 1, the low molecule oxy-compound of 2-naphthoquinones-2-two diazoes-4-sulfonic acid, for example 2,3,4-trihydroxy-benzophenone, 1,3,5-trihydroxybenzene, 2-or 4-methyl-phenol, 4, the ester of 4 '-hydroxyl-propane etc.
When the blending ratio of the diazo naphthoquinone class sensitizer in this positive type photosensitive organic compound is very few, the poor solubility of exposure portion and unexposed portion reduces, even therefore carry out development treatment, can not form the pattern of wanting, in the time of too much, except may be to the film rerum natura (toughness of poly-(imide-azomethine), thermal linear expansion coefficient, second-order transition temperature, thermotolerance etc.) have outside the detrimentally affect, also have behind imidization, the thickness that produces film significantly reduces this class significant problem, therefore with respect to poly-(amido acid-azomethine) multipolymer, by weight, be preferably 10～40%, more preferably 20～30%.
Positive type photosensitive organic compound can contain spendable organic solvent in the described in front operation (I) as required.
This positive type photosensitive organic compound can be made by also dissolving in the organic solvent solution that diazo naphthoquinone class sensitizer is added to poly-(amido acid-azomethine) multipolymer that obtains in the operation (I).
Below, to utilizing this positive type photosensitive organic compound, the method for making the fine pattern of poly-(imide-azomethine) multipolymer describes.
At first, make the positive type photosensitive organic compound film forming.Particularly by the following method: use rotary coating machine or rod to be coated with machine, the coating positive type photosensitive organic compound of solvent cut on substrates such as copper, silicon or glass, under the shading condition, 40～100 ℃ of warm braw dryings 0.1～3 hour, form poly-(amido acid-azomethine) co-polymer membrane of photosensitivity of thickness 1～5 μ m.Preferably carrying out above-mentioned system film below 100 ℃ at this.More than the temperature, diazo naphthoquinone class sensitizer might begin thermolysis at this.In addition, in order to remove residual solvent contained in this co-polymer membrane, also can be 80～100 ℃ of following prebake conditions 1～30 minute, will filming, to flood 1～5 minute in water also be effective.Residual solvent might cause the expansion of film or pattern destroyed when developing, and in order to obtain distinct pattern, preferably fully removes residual solvent.
Then, poly-(amido acid-azomethine) co-polymer membrane of gained photosensitivity is carried out pattern exposure handle, carry out the alkali development treatment then, further carry out polyimide and handle, can be gathered the fine pattern of (imide-azomethine) multipolymer thus.
Specifically can followingly obtain: at room temperature, by photomask to the i ray of poly-(amido acid-azomethine) co-polymer membrane irradiation of photosensitivity high pressure mercury vapour lamp 10 seconds～1 hour, use 0.05～10 weight %, the tetramethylammonium hydroxide aqueous solution of preferred 0.1～5 weight % at room temperature developed 10 seconds～10 minutes, further clean, obtain distinct eurymeric pattern with pure water.Then in air, in the inert gas atmosphere such as nitrogen or in the vacuum, at 200 ℃～430 ℃, preferably under 250 ℃～400 ℃ temperature, the fine pattern of poly-(amido acid-azomethine) multipolymer of forming is carried out hot-imide on substrate and handle, obtain thermal linear expansion coefficient and be lower than 30ppm/K, second-order transition temperature fine pattern at the distinctness of poly-(imide-azomethine) co-polymer membrane more than 250 ℃.
Be noted that imidization also can chemically carry out with cyclodehydration reagent.For example, by at room temperature, will contain the method for 1 minute～a few hours of dipping in the acetic anhydride of basic catalysts such as pyridine or triethylamine at poly-(amido acid-azomethine) co-polymer membrane that forms on the substrate, also can be gathered (imide-azomethine) co-polymer membrane.
Embodiment
Specifically describe the present invention below by embodiment, but the present invention is not subjected to the qualification of these embodiment.In addition, the analytical value in each embodiment and the comparative example is obtained in order to following method.
＜limiting viscosity ([η] dL/g) 〉
Polyimide precursor (poly-(amido acid-azomethine) multipolymer) solution of 0.5 weight % is measured with ostwald's viscometer at 30 ℃.Consider that from the film toughness angle numerical value of expected characteristics viscosity is more than 0.1dL/g.
＜second-order transition temperature (Tg) 〉
The second-order transition temperature of polyimide (poly-(imide-azomethine) multipolymer) film is tried to achieve at loss peak from Measurement of Dynamic Viscoelasticity (frequency 0.1Hz, 5 ℃/minute of heat-up rates).Consider from welding thermotolerance angle, wish that second-order transition temperature (Tg) is more than 250 ℃.
＜5% weight reduces temperature (Td
5)
Measure the thermogravimetric quantitative changeization of polyimide (poly-(imide-azomethine) multipolymer) film in nitrogen atmosphere or in the air atmosphere, try to achieve weight and reduce by 5% temperature.Consider from the thermotolerance angle, wish that 5% weight reduces temperature (Td
5) be more than 400 ℃.
＜thermal linear expansion coefficient (CTE) 〉
Utilize thermo-mechanical analysis,, obtain mean value 100～200 ℃ of scopes as thermal linear expansion coefficient by the elongation of test film under load 0.5g/ thickness 1 μ m, 5 ℃ of/minute conditions of heat-up rate.Consider from the residual stress angle of insulating film/metal substrate of reducing electron device, wish that the numerical value of thermal linear expansion coefficient (CTE:[ppm/k]) is lower than 30ppm/K.
＜double refraction (Δ n) 〉
Be parallel to polyimide film direction (n with Abb (using sodium vapor lamp, wavelength 589nm) mensuration
In) and perpendicular to polyimide film direction (n
Out) specific refractory power, try to achieve double refraction (Δ n=n from their difference of specific refractory power
In-n
Out).The numerical value of double refraction (Δ n) is big more, the orientation degree height of expression polymer chain in face.
＜specific inductivity (ε) 〉
Mean refractive index [n according to polyimide film
Av=(2n
In+ n
Out)/3], through type [ε=1.1 * (n
Av)
2] calculate the specific inductivity (ε) of 1MHz.Consider that from the propagation of electrical signals speed high speed angle of electron device wish that the numerical value of specific inductivity (ε) is low as much as possible, for example as target value, hope is below 3.0.
Embodiment 1 (experiment 1a～1e)
In the closed reaction vessel that has stirrer of thorough drying, with 2,2 '-two (trifluoromethyl) p-diaminodiphenyl (5mmol) be dissolved in abundant dehydration N-N-methyl-2-2-pyrrolidone N-(NMP) or-cresols in, in gained solution, slowly add pyromellitic dianhydride (2mmol then, molar fraction [1-X]=0.4) powder is in 30 minutes～a few hours of stirring at room.Then, add terephthalaldehyde powder (3mmol, molar fraction [X]=0.6) in the gained reaction soln,, obtain thickness and uniformly poly-(amido acid-azomethine) multipolymer stirring at room 24 hours.Carry out polymerization so that monomer concentration is the concentration shown in the table 1 (that is X=0.6～0.9).Measure poly-(amido acid-azomethine) multipolymer of gained in N-N-methyl-2-2-pyrrolidone N-(NMP) 30 ℃ limiting viscosity.In addition, the IR collection of illustrative plates of poly-(amido acid-azomethine) multipolymer of gained is shown in Fig. 1 (azomethine characteristic absorption 1620～1630cm
-1Carboxyl characteristic absorption in the amido acid is at 2600cm
-1About (broad peak)) in.
Then, with poly-(amido acid-azomethine) copolymer solution curtain coating on glass substrate of gained,, obtain fragile a little poly-(amido acid-azomethine) co-polymer membrane 60 ℃ of dryings 2 hours.Under reduced pressure 250 ℃ on substrate with this film hot-imide 2 hours, further carry out thermal treatment in 1 hour at 330 ℃ or 350 ℃, obtaining thickness is transparent and tough poly-(imide-azomethine) co-polymer membrane of 10～20 μ m.
In 2 hours operation of 250 ℃ of hot-imides, confirmed that by infrared ray absorption spectrum shown in Figure 2 hot-imide roughly finishes (the carboxyl characteristic absorption disappearance in the amido acid; Imide carbonyl characteristic absorption 1780cm
-1Azomethine characteristic absorption 1620～1630cm
-1).Owing to next under 330 ℃ or 350 ℃, carry out can't see in the thermal treatment in 1 hour the variation of infrared absorption spectrum, therefore it is generally acknowledged that the thermal treatment under 350 ℃ does not in fact cause structural changes, but this thermal treatment significantly increased the toughness of film.It is generally acknowledged that this is because high-temperature heat treatment makes solid state polymerization (prolongation of polymer chain) takes place between base endways, has increased molecular weight.As mentioned above, measured the rerum natura of various films, demonstrated lower thermal linear expansion coefficient and, be met poly-(imide-azomethine) co-polymer membrane (experiment 1a, 1b and 1d) that requires characteristic than high glass transition.Polymerizing condition and limiting viscosity that multipolymer is formed the scope of [X]=0.6～0.9 are shown in the table 1 (polymerizing condition and the limiting viscosity of poly-(amido acid-azomethine) multipolymer), and the film rerum natura is shown in the table 2 (the film rerum natura of poly-(imide-azomethine) multipolymer).In addition, for experiment 1c and 1e,, do not implement the mensuration of membrane property because film toughness is low.
[table 1]
| Experiment numbers | Form [X] | Polymer solvent | Monomer concentration (weight %) | Polymerization time (hour) | Limiting viscosity [η] (dL/g) |
| 1a | 0.6 | NMP | 37.3 | 24 | 0.166 |
| 1b | 0.7 | NMP | 36.9 | 24 | 0.143 |
| 1c | 0.8 | NMP | 36.5 | 24 | 0.115 |
| 1d | 0.8 | Between-cresols | 24.5 | 24 | 0.167 |
| 1c | 0.9 | Between-cresols | 25.7 | 24 | 0.160 |
[table 2]
| Experiment numbers | Form X | Tg (℃) | CTE (ppm/K) | Δn | ε | T d 5(N 2) (℃) | T d 5(air) (℃) |
| 1a | 0.6 | 336 | 7.9 | 0.107 | 2.94 | 485 | 461 |
| 1b | 0.7 | 355 | 15.6 | 0.111 | 2.95 | 481 | 455 |
| 1c | 0.8 | - | - | - | - | - | - |
| 1d | 0.8 | - | 25.5 | 0.122 | 2.91 | 468 | 445 |
| 1e | 0.9 | - | - | - | - | - | - |
Embodiment 2 (experiment 2a and 2b)
As can be seen from Table 4, can obtain demonstrating lower thermal linear expansion coefficient and than poly-(imide-azomethine) co-polymer membrane (experiment 2a, 2b) of high glass transition, the characteristic that meets the demands.
[table 3]
| Experiment numbers | Form X | Polymer solvent | Monomer concentration (weight %) | Polymerization time (hour) | Limiting viscosity [η] (dL/g) |
| 2a | 0.5 | DMAc | 40.0 | 24 | 0.152 |
| 2b | 0.2 | DMAc | 31.7 | 24 | 0.314 |
[table 4]
| Experiment numbers | Form X | Tg (℃) | CTE (ppm/K) | Δn | ε | T d 5(N 2) (℃) | T d 5(air) (℃) |
| 2a | 0.5 | 348 | 32.7 | 0.064 | 2.83 | 431 | 422 |
| 2b | 0.2 | 343 | 28.1 | 0.042 | 2.77 | 431 | 427 |
Embodiment 3 (experiment 3)
Use anti-form-1, the 4-cyclohexane diamine replaces 2,2 '-two (trifluoromethyl) p-diaminodiphenyl as diamines, use 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride replaces pyromellitic dianhydride as the tetracarboxylic dianhydride, according to the method described in the embodiment 1, will gather (amido acid-azomethine) copolymer polymerization.At first, with anti-form-1,4-cyclohexane diamine 5mmol is dissolved in the N,N-dimethylacetamide, slowly adds 3,3 ', 4, and 4 '-biphenyl tetracarboxylic dianhydride powder 4.5mmol heated 5 minutes at 120 ℃ in oil bath.At room temperature continue stirred for several hour afterwards, obtain thickness and even polyamic acid.In this solution, add terephthalaldehyde powder 0.5mmol (total monomer concentration: 15 weight %), at room temperature stirred 24 hours, gathered (amido acid-azomethine) multipolymer.Limiting viscosity is 0.576dL/g.
Make cast film by poly-(amido acid-azomethine) multipolymer of gained.The transmissivity of this cast film at the wavelength place of the i of high pressure mercury vapour lamp ray (365nm) is more than 70%, demonstrates the high transparency.With the method the same with embodiment 1, make poly-(imide-azomethine) co-polymer membrane, measure the film rerum natura.The film rerum natura is shown in the table 5 (the film rerum natura of poly-(imide-azomethine) multipolymer).As can be seen from Table 5, poly-(imide-azomethine) co-polymer membrane of embodiment 3 (experiment 3) demonstrates lower thermal linear expansion coefficient and than high glass transition, characteristic meets the demands.
[table 5]
| Experiment numbers | Form X | Tg (℃) | CTE (ppm/K) | Δn | ε | T d 5(N 2) (℃) | T d 5(air) (℃) |
| 3 | 0.1 | 300 | 17.8 | 0.143 | 3.10 | 466 | 432 |
N toward poly-(amido acid-azomethine) multipolymer described in the embodiment 3; add 2 in the N-dimethylacetamide solution; 3; 4-three (1-oxo-2-diazo naphthoquinone-5-alkylsulfonyl (ス Le Off オ キ シ)) benzophenone is as diazo naphthoquinone class sensitizer; making its actual amount with respect to poly-(amido acid-azomethine) multipolymer is 30 weight %, and makes it dissolving.It is coated on silane coupling agent has carried out on the surface-treated silicon wafer, 60 ℃ in hot-air drier dry 2 hours, obtain the photosensitive film that thickness is 4～5 μ m.This film after 10 minutes, by photomask, is shone the i ray of 5 minutes reflective high pressure mercury vapour lamps 80 ℃ of following prebake conditions through interference filter.Irradiates light intensity is about 3mW/cm
2About.Under 25 ℃ it was being developed 1～6 minute in the tetramethylammonium hydroxide 0.1 weight % aqueous solution, after water cleans, at 60 ℃ of drying numbers minute.In a vacuum, 250 ℃ 1 hour, further 330 ℃ following 1 hour, progressively heat up, carry out hot-imide, obtain the pattern of the distinctness of live width 20 μ m.
Comparative example 1
In the closed reaction vessel that has stirrer of thorough drying, add 2,2 '-two (trifluoromethyl) p-diaminodiphenyl 4.5mmol and 2, two (4-(4-amino-benzene oxygen) benzene) the HFC-236fa 0.5mmol of 2-are dissolved in it in N-N-methyl-2-2-pyrrolidone N-of abundant dehydration.Add terephthalaldehyde powder 5mmol in this solution,, obtain thickness and poly methylene imine multipolymer uniformly stirring at room 24 hours.Limiting viscosity 30 ℃ of mensuration in the N-N-methyl-2-2-pyrrolidone N-is 0.481dL/g.This poly methylene imine copolymer solution is coated on the glass substrate, 60 ℃ of dryings 2 hours, further on substrate, carries out thermal treatment in 1 hour at 250 ℃, obtaining thickness is the transparent and tough poly methylene imine co-polymer membrane of 10～20 μ m.Second-order transition temperature is 269 ℃, and it is 445 ℃ that 5% weight in nitrogen reduces temperature, demonstrate than higher thermotolerance, but the thermal linear expansion coefficient height is 97ppm/K, fails to obtain required low thermal expansion characteristics.This is because in the casting film process, has only solvent evaporation, and is insufficient as the factor that is orientated in the face that promotes polymer chain.
Comparative example 2
By 2, two (4-(4-amino-benzene oxygen) benzene) HFC-236fa and the pyromellitic dianhydride polymerization polyimide precursors of 2-.Limiting viscosity is 0.696dL/g.This polyimide precursor solution of coating 60 ℃ of dryings 2 hours, further on substrate, is under reduced pressure carried out 1 hour imidization at 250 ℃ on glass substrate, and obtaining thickness is the transparent and tough polyimide film of 10～20 μ m.Second-order transition temperature is 278 ℃, and it is 534 ℃ that 5% weight in nitrogen reduces temperature, demonstrate than higher thermotolerance, but the thermal linear expansion coefficient height is 61ppm/K, fails to obtain required low thermal expansion characteristics.Low from birefringence value, be 0.0093 as can be seen, this high thermal linear expansion coefficient is the reason that causes the polyimide chain to be orientated in face hardly.This is because the diamines that uses is a bendability, does not almost cause the rectilinearity and the rigidity of the indispensable main chain of the interior orientation of face of imidization.
Comparative example 3
According to the method described in the embodiment 3, by anti-form-1,4-cyclohexanediamine and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride polymerization polyimide precursor.Limiting viscosity is 1.50dL/g.Use this polyimide precursor, make the photosensitive polymer combination film by the method described in the embodiment 4, the exposure of trying, alkali develop, but can not form pattern.This is because the solubleness of polyimide precursor in alkaline aqueous solution of using is too high.
Industrial applicability
Poly-(acid imide-azomethine) copolymer of the present invention be by will be as in molecule, introducing of intramolecular cyclization reaction position the amic acid residue polyimide precursor namely poly-(amic acid-azomethine) copolymer imidizate obtain. Therefore, poly-(acid imide-azomethine) copolymer of the present invention is the copolymer of low-thermal-expansion. In addition, the resin combination that is consisted of by poly-(amic acid-azomethine) copolymer and emulsion demonstrate can pattern exposure photonasty, and become the positive type photosensitive organic compound that can alkali develops. Utilize this positive type light sensitive type resin combination, can form have low-k, the fine pattern of poly-(acid imide-azomethine) copolymer of low thermal coefficient of expansion, high glass-transition temperature. Therefore, poly-(acid imide-azomethine) copolymer of the present invention can advantageously be applied in the various electronic devices such as interlayer dielectric of diaphragm, integrated circuit of semiconductor element.
Claims (13)
1. one kind is gathered (imide-azomethine) multipolymer, and it contains the azomethine polymerized unit of formula (1) and the imide polymerized unit of formula (2):
[Chemical formula 1]
In formula (1) and formula (2), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group.
2. described poly-(imide-azomethine) multipolymer of claim 1, wherein, the molar fraction of establishing formula (1) is X, when the molar fraction of establishing formula (2) was 1-X, X was in 0.05～0.95 scope.
3. claim 1 or 2 described poly-(imide-azomethine) multipolymers, its thermal linear expansion coefficient is lower than 30ppm/K, and second-order transition temperature is more than 250 ℃.
4. the manufacture method of described poly-(imide-azomethine) multipolymer of a claim 1, wherein, the diamines of formula (a), the acid dianhydride of formula (b) and the dialdehyde of formula (c) are mixed, and make it polymerization, formation comprises poly-(amido acid-azomethine) multipolymer of the amido acid polymerized unit of the azomethine polymer unit of formula (1) and formula (3), poly-(amido acid-azomethine) multipolymer of gained is carried out imidization to be handled
[Chemical formula 2]
H
2N-A-NH
2 (a)
OHC-D-CHO (c)
In formula (a), formula (b) and formula (c), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group,
[chemical formula 3]
In formula (1) and formula (3), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group.
5. the described manufacture method of claim 4, wherein, the molar fraction of establishing formula (1) is as X, and when the molar fraction of establishing formula (3) was 1-X, X was in 0.05～0.95 scope.
6. claim 4 or 5 described manufacture method, it is that acid dianhydride with the diamines of formula (a) and formula (b) mixes, make it reaction after, with the dialdehyde and the reaction mixture of formula (c), make it reaction.
7. one kind is gathered (amido acid-azomethine) multipolymer, and it comprises the azomethine polymerized unit of formula (1) and the amido acid polymerized unit of formula (3),
[chemical formula 4]
In formula (1) and formula (3), A and D represent the aromatic group or the aliphatic group of divalence respectively, and B represents quaternary aromatic group or aliphatic group.
8. described poly-(amido acid-azomethine) multipolymer of claim 1, wherein, the molar fraction of establishing formula (1) is X, when the molar fraction of establishing formula (3) was 1-X, X was in 0.05～0.95 scope.
9. claim 7 or 8 described poly-(amido acid-azomethine) multipolymers, its limiting viscosity is more than the 0.1dL/g.
10. positive type photosensitive organic compound, it contains any described poly-(amido acid-azomethine) multipolymer and diazo naphthoquinone class sensitizer in the claim 7～9.
11. the described positive type photosensitive organic compound of claim 10, wherein, diazo naphthoquinone class sensitizer is 10～40% with respect to the part by weight of poly-(amido acid-azomethine) multipolymer.
12. the manufacture method of a fine pattern, wherein, by with claim 10 or 11 described positive type photosensitive organic compound system films, gained positive type photosensitive organic compound film is carried out after pattern exposure handles, carry out the alkali development treatment, further carry out the polyimide processing, gathered the fine pattern of (imide-azomethine) multipolymer.
13. the described fine pattern manufacture method of claim 12, wherein, the thermal linear expansion coefficient of poly-(imide-azomethine) multipolymer is lower than 30ppm/K, and second-order transition temperature is more than 250 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP253632/2004 | 2004-08-31 | ||
| JP2004253632A JP4811553B2 (en) | 2004-08-31 | 2004-08-31 | Poly (imide-azomethine) copolymer, poly (amidic acid-azomethine) copolymer, and positive photosensitive resin composition |
| PCT/JP2005/013704 WO2006025163A1 (en) | 2004-08-31 | 2005-07-27 | Poly(imide/azomethine) copolymer, poly(amic acid/ azomethine) copolymer and positive type photosensitive resin compositions |
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| Publication Number | Publication Date |
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| CN101048442A true CN101048442A (en) | 2007-10-03 |
| CN101048442B CN101048442B (en) | 2012-02-29 |
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| CN2005800373468A Active CN101048442B (en) | 2004-08-31 | 2005-07-27 | Poly(imide/azomethine) copolymer, poly(amic acid/azomethine) copolymer and positive type photosensitive resin compositions |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4811553B2 (en) |
| KR (1) | KR20070057898A (en) |
| CN (1) | CN101048442B (en) |
| WO (1) | WO2006025163A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111880371A (en) * | 2020-08-13 | 2020-11-03 | 清华大学 | Photoresist and method for patterning imine material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4858678B2 (en) * | 2005-05-24 | 2012-01-18 | ソニーケミカル＆インフォメーションデバイス株式会社 | Ester group-containing poly (imide-azomethine) copolymer, ester group-containing poly (amide acid-azomethine) copolymer, and positive photosensitive resin composition |
| JP5668517B2 (en) * | 2011-02-16 | 2015-02-12 | 日立化成株式会社 | Thermosetting resin composition, prepreg and laminate |
| JP7156877B2 (en) * | 2018-09-18 | 2022-10-19 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminate and patterned metal-clad laminate |
| JP2020105498A (en) * | 2018-12-26 | 2020-07-09 | 群栄化学工業株式会社 | Polyimine, polyimine-imide, varnish, film and production method of the same, and laminate and production method of the same |
| CN109942815B (en) * | 2019-03-20 | 2021-06-01 | 浙江福斯特新材料研究院有限公司 | Polyimide composite resin with low dielectric constant, preparation method and application |
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| JPS5213235B2 (en) * | 1972-08-16 | 1977-04-13 | ||
| JPH02156655A (en) * | 1988-12-09 | 1990-06-15 | Hitachi Ltd | Semiconductor device |
| JPH03185066A (en) * | 1989-12-14 | 1991-08-13 | Nitto Denko Corp | Thermosetting resin composition |
| JPH05247207A (en) * | 1992-03-06 | 1993-09-24 | Nitto Denko Corp | Heat-resistant resin composition |
| US5409793A (en) * | 1994-04-01 | 1995-04-25 | Xerox Corporation | Polyimide-imine toner and developer compositions |
| JPH08215701A (en) * | 1995-02-10 | 1996-08-27 | Nippon Steel Corp | Manufacture of high toughness thick steel plate without material anisotropy |
| JP3425343B2 (en) * | 1996-10-31 | 2003-07-14 | 株式会社東芝 | Positive photosensitive polymer resin composition, pattern forming method using the same, and electronic component |
| JP2001215701A (en) * | 1999-11-26 | 2001-08-10 | Nitto Denko Corp | Photosensitive resin composition, porous resin, circuit board and suspension substrate with circuit |
| JP3972600B2 (en) * | 2000-09-14 | 2007-09-05 | ソニーケミカル＆インフォメーションデバイス株式会社 | Polyimide precursor, method for producing the same, and photosensitive resin composition |
| JP2003183390A (en) * | 2001-12-19 | 2003-07-03 | Nitto Denko Corp | Photosensitive resin composition and polybenzoxazole resin |
| JP4858678B2 (en) * | 2005-05-24 | 2012-01-18 | ソニーケミカル＆インフォメーションデバイス株式会社 | Ester group-containing poly (imide-azomethine) copolymer, ester group-containing poly (amide acid-azomethine) copolymer, and positive photosensitive resin composition |
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- 2004-08-31 JP JP2004253632A patent/JP4811553B2/en active Active
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111880371A (en) * | 2020-08-13 | 2020-11-03 | 清华大学 | Photoresist and method for patterning imine material |
| WO2022033364A1 (en) * | 2020-08-13 | 2022-02-17 | 无锡华睿芯材科技有限公司 | Photoresist and method for patterning imine material |
| CN111880371B (en) * | 2020-08-13 | 2022-05-03 | 常州华睿芯材科技有限公司 | Photoresist and method for patterning imine material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101048442B (en) | 2012-02-29 |
| WO2006025163A1 (en) | 2006-03-09 |
| KR20070057898A (en) | 2007-06-07 |
| JP2006070117A (en) | 2006-03-16 |
| JP4811553B2 (en) | 2011-11-09 |
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