CN103788653A - Composition for forming underlayer film for image formation - Google Patents

Composition for forming underlayer film for image formation Download PDF

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CN103788653A
CN103788653A CN201410028650.7A CN201410028650A CN103788653A CN 103788653 A CN103788653 A CN 103788653A CN 201410028650 A CN201410028650 A CN 201410028650A CN 103788653 A CN103788653 A CN 103788653A
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polyimide
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composition
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polyimide precursor
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前田真一
小野豪
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Nissan Chemical Corp
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Abstract

A composition for forming an underlayer film for image formation is provided which gives an image-forming underlayer film having high water repellency (hydrophobicity), capable of being easily changed in hydrophilicity/hydrophobicity by exposure even to a small amount of ultraviolet, and having a high relative permittivity. Also provided is a cured film obtained from the composition. The composition for forming an underlayer film for image formation is characterized by containing at least one member selected from the group consisting of a polyimide precursor comprising structural units represented by the following formulae (1) and (1a) and a polyimide obtained by the dehydrating cyclization of the polyimide precursor. (In the formulae, A represents a tetravalent organic group; B1 represents a divalent organic group having fluoroalkyl; B2 represents a divalent organic group; R1, R2, R1a, and R2a each independently represents hydrogen or a monovalent organic group; and n and m each is a positive integer, provided that 0.01<=n/(n+m)<=0.3.)

Description

Be used to form the lower membrane composition of image
The application is that application number is 200980108394.X, the applying date to be the divisional application that on March 10th, 2009, denomination of invention are " being used to form the lower membrane composition of image ".
Technical field
The precursor that the present invention relates to comprise polyimide and/or the precursor dehydration closed-loop of this polyimide and the lower membrane composition that is used to form image of polyimide, and relate to the cured film and the electron device that adopt said composition to manufacture.
Background technology
Proposed in the manufacturing process of electron device, in the time that the pattern of electrode, functional film forms, the pattern that the separately paint-on technique of wettability difference that has utilized liquid is applied to functional film forms.The method is, form and comprise the region easily being soaked by liquid and the pattern form layers that is difficult for the region being soaked by liquid at substrate surface, then on this pattern form layers, be coated with the liquid that forms material containing functional film, then make it dry, only form functional film in the region easily being soaked by liquid thus, thereby manufacture the electron device such as organic EL (electroluminescent) element, organic FET (FET) element.
The image that forms middle use as the pattern of above-mentioned electrode forms liquid, the main PEDOT/PSS aqueous solution that adopts, but because the surface tension of this PEDOT/PSS aqueous solution is higher, be therefore difficult to by method film forming such as method of spin coating, print processes, thereby generally adjust so that surface tension reduces.The image that surface tension is low forms liquid, because the substrate to as film forming object shows the wetting character expanding, therefore in order to suppress, the region of liquid beyond target site is wetting to be expanded, and need to only make target site wetting ability, makes target site area surfaces hydrophobicity in addition.
In recent years, utilize following true broad research and separately applied the technology of application type functional materials, the described fact is the polyimide precursor that can contain hydrophobic side chains by employing or the polyimide being obtained by this polyimide precursor pattern form layers as electrode, functional film etc., and the hydrophilic and hydrophobic of polyimide film is changed, change water contact angle.
For example, explicitly pointed out the characteristic (for example,, with reference to patent documentation 1) that adopts the wettability change layer that there is the polyimide precursor of aliphatics ring or polyimide and obtain.In the document, to infer that the aliphatics ring fracture that polyimide is to cause one of reason that hydrophilic and hydrophobic changes, and infer that the amount (being side chain number) of side chain more, surface is can (critical surface tension) lower, forms lyophobicity.
In addition, in the embodiment of above-mentioned document, in the case of using by having that the acid dianhydride of aliphatics ring and side chain have the diamines of alkyl, the polyamic acid that obtains is as wettability change layer, demonstrate the result that hydrophilic and hydrophobic is significantly changed by uviolizing, and demonstrate the electrode layer that formation comprises PEDOT/PSS in this wettability change layer and manufacture electronic component.
Patent documentation 1: No. 2006/137366 brochure of International Publication
Summary of the invention
Conventionally, can film forming in order to make image form liquid, this image is formed to liquid and design, to make it have the surface tension lower than water.Therefore, consider the easiness of coating, image formation liquid often surface tension lower than the organic solvent of water is.
But, for illustrative hydrophobic side chain in above-mentioned document, even in the case of make the content of side chain fully large, the hydrophobicity (being water-repellancy) that can not say unexposed portion will be fully high, for example, in the situation that image formation hydrorrhea goes out unexposed portion, exist image to form liquid convection drying, and can not obtain the such problem of target image.
In addition, the general relative permittivity of hydrophobic group is lower, the increase of side chain content can cause relative permittivity to reduce, particularly, even if the high fluoroalkyl of hydrophobicity is compared with other hydrophobic group, relative permittivity is also extremely low, therefore exists and does not think for the middle gate insulating films that use such as organic transistor it is preferred such problem.
Therefore, the lower membrane that is used to form image that forms middle use due to the main pattern at the source drain of organic transistor also needs to have both the function as gate insulating film, does not therefore also use polyimide based material that above-mentioned side chain comprises fluoroalkyl as the example of lower membrane that is used to form image.
Therefore, in order to reduce the driving voltage of organic transistor, generally the material of gate insulating film is designed so that its relative permittivity increases, but the content that only increases the side chain that comprises fluoroalkyl in order to improve water-repellancy (hydrophobicity) can make relative permittivity significantly reduce, even if for example utilize high hydrophobicity to describe fine image, the problem that also can exist gate insulator film properties to reduce.That is to say, requirement can suppress the reduction of relative permittivity and obtain the new material with hydrophobic side chains of high water-repellancy.
The present invention proposes in view of the above fact, its object is to provide a kind of lower membrane composition that is used to form image, the lower membrane that is used to form image forming has high water-repellancy (hydrophobicity), even also can easily change hydrophilic and hydrophobic with few ultraviolet exposure amount, and can suppress the reduction of relative permittivity.
In addition, the object of the present invention is to provide a kind of lower membrane composition that is used to form image, for formed lower membrane, the image that adopts the coating processes such as method of spin coating, ink jet printing method to be coated with using low surface tension solvent as main solvent forms liquid, can form the pattern (image formation) of fine.
In addition, the object of the present invention is to provide and can be below 200 ℃ toast at the temperature of (below 180 ℃), and electrical insulating property, the lower membrane formation composition that is used to form image that chemical stability is high, and insulativity excellence, the good effective gate insulating film of organic crystal of characteristic that gate leakage currents is few.
The present inventors have carried out further investigation repeatedly to achieve these goals, found that, by importing the phenyl with fluoroalkyl with the scope that is not more than 30 % by mole in the structure of the polyimide that obtains to polyimide precursor and/or by this polyimide precursor, not only can hydrophilic/hydrophobic significantly be changed by uviolizing thus, and can give high water-repellancy, and can not cause the reduction of relative permittivity, thereby complete the present invention.
; as the 1st viewpoint of the present invention; relate to a kind of lower membrane composition that is used to form image; it is characterized in that; comprise and be selected from that polyimide precursor and this polyimide precursor carry out dehydration closed-loop and at least one compound in the polyimide that obtains; described polyimide precursor comprises following formula (1) and the represented structural unit of formula (1a)
Figure BDA0000459641930000031
In above formula, A represents 4 valency organic groups, B 1represent at least a kind of divalent organic group that following formula (2) is represented, B 2represent divalent organic group, R 1, R 2, R 1a, R 2arepresent independently of one another hydrogen atom or 1 valency organic group, n is the total mole number of the represented structural unit of formula (1), m is the total mole number of the represented structural unit of formula (1a), and n and m represent respectively positive integer and meet 0.01≤n/ (n+m)≤0.3
Figure BDA0000459641930000041
In above formula, X 1represent singly-bound ,-O-,-COO-,-OCO-,-CONH-,-CH 2o-, X 2represent the divalent organic group that carbonatoms is 3～18, R 3represent the perfluoroalkyl that carbonatoms is 2～12.
As the 2nd viewpoint, according to the lower membrane composition that is used to form image described in the 1st viewpoint, in above-mentioned formula (1a), B 2at least one the group being selected from following formula (3)～(5),
Figure BDA0000459641930000042
In above formula, Y 1represent independently of one another the alkylenedioxy group can with branched structure that the alkylidene group can with branched structure that singly-bound, ehter bond, ester bond, thioether bond, amido linkage, carbonatoms are 1～3 or carbonatoms are 1～3, Y 2represent singly-bound, ehter bond, ester bond, thioether bond, amido linkage, R 4represent independently of one another hydrogen atom, methyl, ethyl, trifluoromethyl, R 5represent hydrogen atom, methyl, trifluoromethyl, R 6represent methylene radical, ethylidene, j represents 0 or 1 independently of one another.
As the 3rd viewpoint, according to the lower membrane composition that is used to form image described in the 1st viewpoint or the 2nd viewpoint, in above-mentioned formula (1) and formula (1a), 4 represented valency organic groups of A are at least one groups that are selected from following formula (6)～(11)
Figure BDA0000459641930000051
In above formula, R 7, R 8, R 9, R 10represent that independently of one another hydrogen atom, fluorine atom or carbonatoms are 1～4 alkyl.
As the 4th viewpoint, according to the lower membrane composition that is used to form image described in any one of the 1st viewpoint～3rd viewpoint, the polyimide precursor that comprises the represented structural unit of above-mentioned formula (1) and formula (1a) and this polyimide precursor carry out dehydration closed-loop and the polyimide that obtains, the represented tetracarboxylic dianhydride of following formula (16) and following formula (17) and two represented amine components of (18) to be reacted and the polyimide precursor and the polyimide that obtain
Figure BDA0000459641930000052
In above formula, A, B 1and B 2identical with the definition in above-mentioned formula (1) and formula (1a).
As the 5th viewpoint, a kind of lower membrane that is used to form image, adopts the lower membrane composition that is used to form image described in any one of the 1st viewpoint～4th viewpoint to obtain.
As the 6th viewpoint, a kind of lower membrane that is used to form electrode pattern, adopts the lower membrane composition that is used to form image described in any one of the 1st viewpoint～4th viewpoint to obtain.
As the 7th viewpoint, the effective gate insulating film of a kind of organic crystal, adopts the lower membrane composition that is used to form image described in any one of the 1st viewpoint～4th viewpoint to obtain.
As the 8th viewpoint, be to adopt the effective gate insulating film of organic crystal described in the 7th viewpoint and the organic transistor that obtains.
The lower membrane composition that is used to form image that comprises at least one compound in the polyimide that is selected from polyimide precursor and obtained by this polyimide precursor of the present invention, for the film being formed by this lower membrane composition that is used to form image, by causing that large contact angle changes, i.e. the variation of hydrophilic and hydrophobic to having adopted take the solvent of low surface tension as the image formation liquid of main solvent carries out uviolizing.Therefore, can utilize such characteristic to form lower membrane, the image that described lower membrane can be carried out functional materials such as electrode etc. forms.
In addition the cured film being formed by composition of the present invention, can form the lower membrane that is used to form image that relative permittivity is high.The lower membrane of what relative permittivity was high be used to form image also can be used as the effective gate insulating film of organic crystal.In addition the lower membrane that is used to form image that, relative permittivity is high can reduce the driving voltage of organic transistor.
In addition, because not only can adopting ink jet method to be coated with image, the cured film being formed by composition of the present invention forms liquid, can also adopt the several different methods such as rotary coating, pickling process to be coated with image and form liquid, therefore this cured film is effective material aspect productivity.
Embodiment
The present invention is the lower membrane composition that is used to form image that contains at least one compound being selected from the polyimide that has the polyimide precursor of new structure and obtained by this polyimide precursor.In addition, relate to the cured film (being used to form the lower membrane of image, the lower membrane that is used to form electrode pattern, the effective gate insulating film of organic crystal) that adopts above-mentioned composition and obtain, and relate to the electron device that adopts this cured film.
Below, be elaborated.
[polyimide precursor and the polyimide being obtained by this polyimide precursor]
The present invention is the lower membrane composition that is used to form image, comprise and be selected from that polyimide precursor and this polyimide precursor dewater open loop and at least one compound in the polyimide that obtains, described polyimide precursor comprises following formula (1) and the represented structural unit of formula (1a).
Figure BDA0000459641930000061
(in above formula, A represents 4 valency organic groups, B 1represent at least a kind of divalent organic group that above-mentioned formula (2) is represented, B 2represent divalent organic group, R 1, R 2, R 1a, R 2arepresent independently of one another hydrogen atom or 1 valency organic group, n is the total mole number of the represented structural unit of formula (1), m is the total mole number of the represented structural unit of formula (1a), and n and m represent respectively positive integer and meet 0.01≤n/ (n+m)≤0.3.)
In above-mentioned formula (1) and formula (1a), the structure of the represented organic group of A does not just limit especially as long as 4 valency organic groups.In addition, in at least one compound in the polyimide that is selected from the represented polyimide precursor of formula (1) and formula (1a) and obtained by this polyimide precursor, the structure of the represented organic group of A can be a kind, also can multiple mixing exist.
As the concrete example of the represented organic group of A, can enumerate the organic group of following formula A-1～A-36.
Figure BDA0000459641930000071
Figure BDA0000459641930000081
In above-mentioned formula A-1～A-36, in the time being formed for forming the lower membrane of image, can suitably select according to desired characteristic.
For example, in above-mentioned formula A-1～A-36, for A-1～A-11, form polyimide at the polyimide precursor of contained (1) and the represented structural unit of formula (1a), can think, due to aromatic ring and the direct combination of imide ring, therefore insulativity reduces (Leakage Current is large), but compared with the situation of aliphatics ring and the direct combination of imide ring, there is relative permittivity and increase such feature.
On the other hand, for A-12～A-35, owing to thering is alicyclic structure in group, therefore from not only can improving insulativity (Leakage Current is little), can also reduce following contact angle and change the viewpoint of required ultraviolet irradiation amount, preferred, particularly preferably A-12～A-15.
In addition, A-17, A-27, A-29, A-30, A-31, A-32 or A-36 etc. change required ultraviolet irradiation amount owing to can reducing contact angle, and higher to the solvability of solvent in the time forming polyimide, therefore most preferably.In addition,, in order to improve the required ultraviolet irradiation amount of variation of solvability and minimizing hydrophilic and hydrophobic, can use the 4 valency organic groups with alicyclic structure by multiple combination.
In above-mentioned formula (1), B 1be the divalent organic group with fluoroalkyl, represent particularly at least a kind of divalent organic group that following formula (2) is represented.
Figure BDA0000459641930000091
(in above formula, X 1represent singly-bound ,-O-,-COO-,-OCO-,-CONH-,-CH 2o-, X 2represent the divalent organic group that carbonatoms is 3～18, R 3represent the perfluoroalkyl that carbonatoms is 2～12.)
Above-mentioned R 3represented fluoroalkyl, although surface free energy is less, can give high water-repellancy, if but carbonatoms is less than 2, can not obtain high water-repellancy, if carbochain is long, is not only difficult to control water-repellancy and relative permittivity and can reduces etc., based on this reason, preferably carbonatoms is 2～12, more preferably 4～8.
In addition, can be by making the increase of fluorine content obtain higher water-repellancy, but the structure that chain alkyl has all been fluorinated can cause that relative permittivity significantly reduces on the contrary.
Therefore, can by use the carbochain such as alkylidene group that do not contain fluorine atom as linking group (in formula (2), X 2), suppress the reduction of relative permittivity, and obtain high hydrophobicity.
X 2that carbonatoms is 3～18 divalent organic group, the divalent organic group that more preferably carbonatoms is 6～18, most preferably carbonatoms is 9～18.
X 2as long as the divalent organic group that carbonatoms is 3～18, its structure is not just limited especially, be preferably selected from alkylidene group, there is aromatic ring or aliphatics ring or the two divalent alkyl.
In formula (2), above-mentioned X 2can with the direct combination of phenyl ring, also can be situated between by conjugated group combination., in formula (2), as X 1, can enumerate singly-bound ,-O-,-COO-,-OCO-,-CONH-,-CH 2o-.
As the B of the represented divalent organic group of above-mentioned formula (2) 1concrete example, can enumerate following formula (12)～(15).
Figure BDA0000459641930000101
It should be noted that, can think that the contact angle variation that demonstration wetting ability-hydrophobicity changes is because uviolizing makes B in formula (1) 1fluorine-containing side chain decompose caused.And known, 4 represented valency organic groups of above-mentioned A also decompose by ultraviolet ray, thereby make contact angle significantly change (patent documentation 1).
In above-mentioned general formula (1), B 1the represented divalent organic group with fluoroalkyl (the represented group of formula (2)) is even if also can give on a small quantity high water-repellancy.But if content is too much, relative permittivity can reduce, in addition, the variable quantity of the hydrophilic and hydrophobic causing by ultraviolet irradiation also can reduce, and therefore merges and uses following B 2represented divalent organic group.
In above-mentioned formula (1a), B 2be divalent organic group, be preferably and meet following such organic group that requires.
In the past, imported long-chain side chain in order to give water-repellancy, but as mentioned above, B 1fluoroalkyl in group, just can give high water-repellancy on a small quantity, therefore can reduce the importing ratio of long-chain side chain.
Therefore, from giving water-repellancy, that is, reduce the such viewpoint of surface free energy and set out, due to the chain alkyl not needing beyond fluoroalkyl, also can not reduce relative permittivity, therefore preferably do not contain.
It should be noted that, from expecting to improve density, the such viewpoint of raising sensitivity of contact angle variation portion (acid anhydrides composition), the reduction of the importing ratio of long-chain side chain is also preferred.In this manual, sensitivity refers to the degree changing from hydrophobicity to wetting ability of unit exposure amount (ultraviolet irradiation amount).
, from meeting above-mentioned condition and effectively absorbing ultraviolet ray, effectively carry out contact angle and change such viewpoint, B 2represented divalent organic group preferably has aromatic ring.For example, be preferably following formula (3)～(5) represented organic group.
Figure BDA0000459641930000111
(in above formula, Y 1represent independently of one another the alkylenedioxy group can with branched structure that the alkylidene group can with branched structure that singly-bound, ehter bond, ester bond, thioether bond, amido linkage, carbonatoms are 1～3 or carbonatoms are 1～3, Y 2represent singly-bound, ehter bond, ester bond, thioether bond, amido linkage, R 4represent independently of one another hydrogen atom, methyl, ethyl, trifluoromethyl, R 5represent hydrogen atom, methyl, trifluoromethyl, R 6represent methylene radical, ethylidene, j represents 0 or 1 independently of one another.)
As above-mentioned formula (3)～(5) represented B 2concrete example, can enumerate the divalent organic group of following B-1～B-23.
Figure BDA0000459641930000112
Wherein, B-2, B-3, B-5, B-10, B-13, because solvability is high, can manufacture the soluble polyimide that solvability is high, thereby more preferably.
In addition, from the viewpoints such as solvability, minimizing exposure, B 2represented divalent organic group can two or more be used in combination.In addition, the scope not reducing at relative permittivity, also can be used other divalent organic group with chain alkyl side chain.
As mentioned above, in above-mentioned general formula (1), if B 1the content of the fluoroalkyl comprising in group is too much, can cause the reduction of the reduction of relative permittivity and the variable quantity of the hydrophilic and hydrophobic that ultraviolet irradiation causes, therefore also uses above-mentioned B 2represented divalent organic group.
But if the content of fluoroalkyl is very few, the water-repellancy of unexposed portion can reduce, thereby can not make the image that surface tension is low form liquid formation pattern.
Therefore, B 1with B 2containing proportional,, in formula (1), the ratio of represented m in represented n and formula (1a), is preferably 0.01≤n/ (n+m) <0.1, most preferably is the scope of 0.01≤n/ (n+m) <0.06.
" manufacture method of polyimide precursor "
In order to obtain the polyimide precursor that comprises above-mentioned formula (1) and the represented structural unit of formula (1a), easy method is that the represented tetracarboxylic dianhydride's composition of following formula (16) and following formula (17) and two represented amine components of (18) are mixed in organic solvent.It should be noted that, these tetracarboxylic dianhydride's compositions and two amine components can use respectively one or two or more kinds.
Figure BDA0000459641930000131
(in above formula, A is 4 valency organic groups, B 1the represented divalent organic group of above-mentioned general formula (2), B 2represent B 1divalent organic group in addition.)
In the represented tetracarboxylic dianhydride's composition of above-mentioned formula (16), the concrete example of the represented 4 valency organic groups of A can be enumerated the organic group shown in above-mentioned formula A-1～A-36.
In above-mentioned formula (17) or (18) represented two amine components, B 1be the divalent organic group that comprises fluoroalkyl, specifically can enumerate above-mentioned formula (12)～(15) represented group.In addition B, 2the concrete example of represented divalent organic group can be enumerated the group shown in above-mentioned formula B-1～B-23.
As mentioned above, A preferably comprises the organic group of the 4 valency organic groups that contain aliphatics ring in a large number, that is, tetracarboxylic dianhydride's composition is the large composition of ratio of aliphatic acid dianhydride preferably.
This be because, adopting aromatic anhydride to manufacture polyimide precursor etc., form in the situation of cured film, if apply high electric field to this cured film, insulativity can significantly reduce, but the insulativity excellence of aliphatic anhydride in high electric field.
The operation voltage of for example organic transistor is often 1MV/cm left and right, the in the situation that of this purposes, from the viewpoint of insulativity, preferably uses the raw material of aliphatic anhydride as polyimide precursor.
As the method that above-mentioned tetracarboxylic dianhydride's composition is mixed in organic solvent with two amine components, can be listed below method: two amine components are dispersed or dissolved in organic solvent, the solution of gained is stirred, directly add tetracarboxylic dianhydride's composition or tetracarboxylic dianhydride's composition is dispersed or dissolved in to the method for then adding in organic solvent; Make conversely tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent, to the method for adding two amine components in the solution of gained; Alternately add the method for tetracarboxylic dianhydride's composition and two amine components etc.
In addition, for the multiple compounds of tetracarboxylic dianhydride's composition and two amine components, these Multiple components can be carried out to polyreaction under the state being pre-mixed, also can carry out successively respectively polyreaction.
In the situation that the above-mentioned polyimide precursor using is in the present invention manufactured by the represented tetracarboxylic dianhydride's composition of above-mentioned formula (16) and above-mentioned formula (17) and (18) represented diamines, the proportioning of two compositions,, the total mole number > of < tetracarboxylic dianhydride composition: the total mole number > of < bis-amine components is preferably 1:0.5～1:1.5.Same with common polycondensation, this mol ratio more approaches 1:1, and the polymerization degree of the polyimide precursor of generation is larger, and molecular weight is larger.
In the manufacture method of above-mentioned polyimide precursor, temperature when tetracarboxylic dianhydride's composition is reacted in organic solvent with two amine components is generally-20～150 ℃, is preferably 0～80 ℃.
If set temperature of reaction for high temperature, polyreaction is carried out rapidly and is finished, if but temperature of reaction is too high, sometimes can not obtain the polyimide precursor of high molecular.
In addition, for the polyreaction of carrying out in organic solvent, the solid component concentration of two compositions in solvent (tetracarboxylic dianhydride's composition and two amine components) is not limited especially, if concentration is too low, be difficult to obtain the polyimide precursor of high molecular, if excessive concentration, the viscosity of reaction solution is too high and be difficult to uniform stirring, therefore be preferably 1～50 quality %, more preferably 5～30 quality %.The polyreaction initial stage carries out under high density, generates polymkeric substance (polyimide precursor) simultaneously, then can add organic solvent.
The organic solvent using when above-mentioned reaction is as long as dissolving the just not restriction especially of organic solvent of the polyimide precursor generating, if enumerate concrete example, can enumerate N, dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone etc.These organic solvents can use separately, also can more than two kinds mix use.In addition,, even the solvent of insoluble solution polyimide precursor, the scope of not separating out at the polyimide precursor generating, also may be combined in above-mentioned solvent.
The solution that comprises polyimide precursor obtaining thus can be directly used in the following underlayer film for image formation coating fluid of preparation.In addition also can, by polyimide precursor precipitate and separate in the poor solvents such as water, methyl alcohol, ethanol, then recycle.
" to the conversion of polyimide "
The polyimide precursor with the represented structural unit of general formula (1) and formula (1a) can form polyimide by dehydration closed-loop.The method of this imidization reaction is not limited especially, but adopt the catalysis imidization of basic catalyst and acid anhydrides, owing to being difficult for causing that the molecular weight of polyimide reduces when the imidization reaction, and easily control imide rate, therefore preferred.
Above-mentioned polyimide precursor can be stirred and within 1～100 hour, carries out catalysis imidization in organic solvent under the existence of basic catalyst and acid anhydrides.
It should be noted that, herein, polyimide precursor can directly (not separate) and adopt the solution that comprises the polyimide precursor being obtained by the polymerization of above-mentioned tetracarboxylic dianhydride's composition and two amine components.
As basic catalyst, can enumerate pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc.Wherein, pyridine is due to the appropriateness alkalescence having for reacting, therefore preferred.
As acid anhydrides, can enumerate diacetyl oxide, TMA, pyromellitic anhydride etc.Wherein, diacetyl oxide is due to after finishing at imidization, and the easy purifying of polyimide obtaining is therefore preferred.
As organic solvent, can use the solvent using in the time of the polyreaction of above-mentioned polyimide precursor.
Temperature of reaction when catalysis imidization is preferably-20～250 ℃, more preferably 0～180 ℃.If temperature of reaction is set high temperature for, imidization carries out rapidly, and if temperature of reaction is too high, the molecular weight of polyimide reduces sometimes.
The amount of basic catalyst is preferably 0.5～30 mole doubly with respect to the amido in above-mentioned polyimide precursor, more preferably 2～20 moles times.In addition, the amount of acid anhydrides is preferably 1～50 mole doubly with respect to the amido in above-mentioned polyimide precursor, more preferably 3～30 moles times.
Can control by adjusting above-mentioned temperature of reaction and catalytic amount the imide rate of the polyimide of gained.
Although can being directly used in, the reaction soln of the solvent-soluble polyimide obtaining as mentioned above manufactures following gate insulating film, but owing to comprising imidization catalyst etc. in reaction solution, therefore preferably polyimide purifying is reclaimed to washing, then for the manufacture of film.
For the recovery of polyimide, easy method is in lower poor solvent, to drop into reaction solution polyimide is precipitated to stirring, and is filtered out.
As the poor solvent now using, do not limit especially, can illustrate methyl alcohol, hexane, heptane, ethanol, toluene, water etc.Preferably after sedimentation and filtration is reclaimed, with above-mentioned poor solvent washing.
The polyimide that recovery can be obtained, under normal pressure or decompression, is prepared polyimide powder at normal temperature or heat drying.
And then this polyimide powder is dissolved in good solvent, in poor solvent, carry out redeposition, this operation is repeated 2～10 times, just can further reduce the impurity in polymkeric substance.
As the good solvent now using, can enumerate N, dinethylformamide, N,N-dimethylacetamide, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl-urea, pyridine, gamma-butyrolactone etc.These good solvents can be used alone, but also also mix together.
In addition,, as the poor solvent using, if use the more than 3 kinds poor solvents such as such as alcohols, ketone, hydrocarbon, just can further improve purification efficiency in redeposition.
[being used to form the lower membrane composition of image]
The lower membrane composition that is used to form image of the present invention is to contain above-mentioned polyimide precursor and/or above-mentioned polyimide and solvent, can also contain as required the composition of following coupling agent, tensio-active agent etc.
For the above-mentioned polyimide precursor that uses in the lower membrane composition of image and/or the molecular weight of polyimide of being used to form of the present invention, the viewpoint of the solvent resistance equistability during from processing ease, film formation, preferably adopt in weight-average molecular weight (adopting the measurement result of GPC) and be preferably 2,000～200,000, more preferably 5,000～50,000 polyimide precursor and/or polyimide.
Manufacture cured film when adopting the lower membrane composition that is used to form image of the present invention, and when irradiation ultraviolet radiation, about the variable quantity of hydrophilic and hydrophobic, between polyimide precursor and polyimide, there is no bigger difference, therefore for gained cured film, in the situation that this respect is placed on to emphasis, imide rate is not limited especially.
But, due to by using polyimide can obtain following advantage, therefore more preferably adopting polyimide, described advantage is: can adopt the low-temperature bake (180 ℃ are following) adapting with plastic base to obtain the film that reliability is high; Compared with polyimide precursor, the polarity of polyimide is low, can increase water contact angle (can improve hydrophobicity) before uviolizing etc.
For the lower membrane composition that is used to form image of the present invention, suppose to form electrode that organic transistor uses as main application, not only require as the function of lower membrane that is used to form image, but also require high-insulativity.
Therefore, for example, using in the cured film (gate insulating film) that insulativity is placed on to emphasis, the polyimide that preferably polyimide precursor is carried out to imidization and obtain is directly dissolved in solvent, makes the lower membrane formation composition that is used to form image.
In this situation, if imide rate is high, solvent solubility is low, but not destroying in deliquescent scope, imide rate is more high more preferred, is specially more than 80%, more preferably more than 90%.
It should be noted that, in the present invention, imide rate refers to polyimide is dissolved in to d 6-DMSO (dimethyl sulfoxide (DMSO)-d 6) in, measure 1h-NMR, obtains imidization not and the ratio of remaining acid amides acidic group (ア ミ De acidic group) by the ratio of amide proton number and aromatic protons number, and calculates imide rate.
As the solvent using in the lower membrane composition of image that is used to form of the present invention, as long as can dissolve polyimide precursor or polyimide, just without particular limitation of, as the example, can enumerate N, the good solvents such as dinethylformamide, N,N-dimethylacetamide, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl-urea, pyridine, gamma-butyrolactone.These solvents can use separately one, also can mix use, and then the poor solvents such as alcohols, ketone, hydrocarbon can also be mixed to use with above-mentioned good solvent.
Ratio for the polyimide precursor in the lower membrane composition that is used to form image of the present invention and/or polyimide with respect to total mass, as long as polyimide precursor and/or polyimide are dissolved in solvent equably, just do not limit especially, be for example 1～30 quality %, or be for example 5～20 quality %.
The compound method of the lower membrane composition that is used to form image of the present invention is not limited especially, can directly use the solution that comprises the polyimide precursor being obtained by the polymerization of above-mentioned tetracarboxylic dianhydride's composition and two amine components, or adopt the reaction soln of the polyimide being obtained by this solution.
In addition,, for the lower membrane composition that is used to form image of the present invention, in order to improve the adhesivity of said composition and substrate, only otherwise destroy effect of the present invention, can also contain coupling agent.
As above-mentioned coupling agent, can enumerate the compound containing functional silanes, containing the compound of epoxy group(ing), specifically can be listed below compound: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-trimethoxy-silylpropyl diethylenetriamine, N-triethoxysilylpropyltetrasulfide diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTESs of N-, ethylene glycol bisthioglycolate glycidyl ether, polyoxyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthenes of 1,3-, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
These coupling agents can use separately one, also can two kinds be used in combination above.
In the situation that using this coupling agent, the lower membrane composition that is preferably used to form image take its content with respect to 100 mass parts is 0.1～30 mass parts, more preferably 1～20 mass parts interpolation.
In addition,, for film uniformity, the surface smoothness of the film that improves the coating of said composition, obtained by said composition, in the lower membrane composition that is used to form image of the present invention, also can contain tensio-active agent.
As above-mentioned tensio-active agent, do not limit especially, for example can enumerate, fluorine is that tensio-active agent, silicone type surface active agent, nonionic are tensio-active agent etc.As this kind of tensio-active agent, for example can enumerate, エ Off ト ッ プ EF301, EF303, EF352 ((strain) ジ ェ system コ system)), メ ガ Off ァ ッ Network F171, F173, R-30 (large Japanese イ Application キ chemical industry (strain) system), Off ロ ラ ー De FC430, FC431 (Sumitomo ス リ ー エ system (strain) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (strain)) etc.
In the situation that using this tensio-active agent, its content is preferably 0.01～2 mass parts, more preferably 0.01～1 mass parts with respect to being used to form component of polymer 100 mass parts that contain in the lower membrane composition of image.
[about polymer blend]
Except polyimide precursor of the present invention and/or polyimide, in the lower membrane composition that is used to form image of the present invention, can also mix other polymkeric substance (for example high-insulativity polymkeric substance) that can form film, and form the form of so-called polymer blend.
For this polymer blend, due to structure of the polymkeric substance that can contain by suitable adjustment (polyimide precursor of the present invention, polyimide and other polymkeric substance) etc., the concentration gradient that produces each polymkeric substance in the time forming cured film along the thickness direction in film, therefore can be used as useful method and utilizes.
For example, what become problem due to the variation of hydrophilic and hydrophobic is only film surface, and therefore from this viewpoint, the polyimide precursor with fluoroalkyl of the present invention and/or polyimide can exist only in the upper strata (upper layer) of cured film.
Therefore, be polymer blend form at the above-mentioned lower membrane composition that is used to form image, as the mixing ratio of polyimide precursor of the present invention or polyimide, be 1 quality %～100 quality % with respect to the total mass of the polymkeric substance after blending.Below 1 quality %, polyimide precursor of the present invention or the polyimide of the most surface of the film that formed are very few if, and image forms ability may be deteriorated.
The useful situation of above-mentioned polymer blend for example can be enumerated the lower membrane composition of image that is used to form of the present invention for the situation of the gate insulating film purposes of special requirement high-insulativity.
For gate insulating film purposes in the situation that, require: this coating fluid adapts with 180 ℃ of following storing temperatures, can be by being coated with the multifrequency nature such as film forming, solvent resistance to organic semiconductor coating fluid non-polar solvents such as () dimethylbenzene, Three methyl Benzenes, low water absorption, particularly require performance high for insulativity.In order to realize this high-insulativity, the imide rate of the lower membrane composition that is used to form image of the present invention is at least more than 80%, and it is more than 90%, on the other hand that difference according to circumstances requires sometimes, if imide rate is greater than 90%, the solubleness of solvent is reduced sometimes.Now, the layer of high-insulativity is only positioned at the orlop of this insulating film, and the layer being formed by the lower membrane composition that is used to form image of the present invention is positioned at upper strata, keeps thus the high-insulativity of this insulating film, and also can solve deliquescent problem.
As mentioned above, be high insulation in order to make the lower floor of cured film, upper strata is hydrophilic and hydrophobic transform layer, also these layers successively lamination can be manufactured, but complicated operation.
Now, the material of high insulation is mixed with the material (being polyimide precursor of the present invention and/or polyimide) of hydrophilic and hydrophobic transform layer, now, if polarity or the molecular weight of the material on upper strata are less than lower floor, mixed solution is being coated on substrate, dry with during evaporating solvent, the material that shows upper strata moves to surface and therefore cambial behavior can easily control above-mentioned concentration gradient (being called layer herein separates).
As the formation material of film of high-insulativity that can form above-mentioned lower floor, most preferably soluble polyimide.In the situation that using soluble polyimide as subsurface material, from the viewpoint of insulativity, the imide rate of the polyimide in preferred solution is higher, is at least more than 50%, is preferably more than 80%, most preferably is more than 90%.
As can, as other material of subsurface material, enumerating the general organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinylphenol, polyisobutene, polymethylmethacrylate.
In addition, be the organic transistor purposes of 400nm left and right in the case of above-mentioned polymer blend being used for requiring for example thickness, upper strata (hydrophilic and hydrophobic transform layer) arrange required polyimide precursor of the present invention and/or polyimide in this polymer blend containing proportional be 1% left and right in theory, if very few, in the face of cured film surface physical property, uneven degree increases, and therefore preferably contains more than at least 5% this polyimide precursor and/or polyimide.
[manufacture method of film and cured film]
Smear by pickling process, method of spin coating, hectographic printing method, rolling method, ink jet method, spray method, bristle etc., on plastic base, the glass substrate etc. generally using at polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, polyethersulfone, PEN, polyimide etc., be coated with the lower membrane composition that is used to form image of the present invention, then carry out predryingly with hot plate or baking oven etc., can form thus film.Then, form can be used as and be used to form the cured film that the lower membrane, insulating film of image are used by this film being carried out to heat treated.
To the method for above-mentioned heat treated without particular limitation of, can illustrate and adopt hot plate, baking oven, under suitable atmosphere,, under the inert gas atmosphere such as atmosphere, nitrogen, wait in a vacuum the method for carrying out heat treated.
From promoting the viewpoint of hot-imide of polyimide precursor, storing temperature is preferably 180 ℃～250 ℃, from can be on plastic base the such viewpoint of film forming, more preferably below 180 ℃.
Can there is temperature variation more than 2 steps in baking.Can toast by substep the homogeneity of the film that further improves gained.
In addition, in the time manufacturing cured film, be the form that comprises polyimide precursor and/or polyimide and above-mentioned solvent owing to being used to form the lower membrane composition of image, therefore can be directly used in to base plate coating, but for adjust concentration or in order to ensure the flatness of film, improve the wettability of coating fluid to substrate, the surface tension of adjusting coating fluid, polarity, boiling point etc., can also add above-mentioned solvent and other all kinds of SOLVENTS, use as coating fluid.
As the concrete example of such solvent, except the solvent above-mentioned paragraph (0071) Suo Shu, can also enumerate ethyl cellosolve, ethylene glycol butyl ether, ethyl carbitol, diethylene glycol monobutyl ether, ethyl carbitol acetic ester, ethylene glycol etc., 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, mono-ethyl ether-the 2-of propylene glycol-1-acetic ester, dipropylene glycol, 2-(2-methoxy propoxy) propyl alcohol, the propanediol derivatives such as 2-(2-oxyethyl group propoxy-) propyl alcohol and 2-(2-butoxy propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, the lactic acid derivativess such as isoamyl lactate etc.These solvents can use separately, also can be used together.
It should be noted that, from improving the viewpoint of film uniformity of keeping quality, film of the lower membrane composition that is used to form image, preferably 20～80 quality % of total solvent amount are for being selected from N, at least a kind of solvent in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, gamma-butyrolactone, dimethyl sulfoxide (DMSO).
Concentration to the lower membrane composition that is used to form image does not limit especially, as the solid component concentration of polyimide precursor and polyimide, is preferably 0.1～30 quality %, more preferably 1～10 quality %.This concentration is set arbitrarily according to the specification of apparatus for coating, the thickness that will obtain.
When using as mentioned above manufacture cured film of the present invention as be used to form image lower membrane use time, if thickness is excessively thin, the pattern formative after uviolizing reduce, if blocked up, surface homogeneity destroyed.Therefore, as its thickness, be preferably 5nm～1000nm, more preferably 10nm～300nm, most preferably is 20nm～100nm.
In addition,, in the situation that insulativity is fully high, cured film of the present invention also can be used as insulating film and plays a role.In this case, in organic FET element for example, this cured film can directly be configured on gate electrode and use as gate insulating film.Now, in order to ensure insulativity, compared with situation about using as the above-mentioned lower membrane that is used to form image, the thickness of this cured film is preferably thicker.As its thickness, be preferably 20nm～1000nm, more preferably 50nm～800nm, most preferably is 100nm～500nm.
[use of lower membrane as being used to form image: the manufacture method that is used to form the electrode of image]
The lower membrane that is used to form image of the present invention, with pattern-like irradiation ultraviolet radiation, is then coated with following image and forms liquid, can manufacture thus the electrode that is used to form image.
In the present invention, the above-mentioned lower membrane that is used to form image is not limited especially with the method for pattern-like irradiation ultraviolet radiation, can enumerate method, the method that employing laser is drawn electrode pattern etc. of for example irradiating by describing the mask of electrode pattern.
As aforementioned mask, its material, shape are not limited especially, as long as need the region of electrode to see through ultraviolet ray, region in addition does not see through ultraviolet ray.
Now, generally can use the ultraviolet ray with 200nm～500nm range of wavelength to irradiate, preferably select suitable wavelength according to the kind of the polyimide of use by wave filter etc.Specifically can enumerate 248nm, 254nm, 303nm, 313nm, 365nm equiwavelength.Be particularly preferably 248nm, 254nm.
The lower membrane that is used to form image of the present invention, due to ultraviolet irradiation, can rise gradually in its surface, and saturated along with sufficient irradiation dose.The contact angle that the rising of this surface energy causes image to form liquid reduces, and result can improve the wettability of the image formation liquid of uviolizing portion.
Therefore, in the time being coated with image formation liquid in the lower membrane that is used to form image of the present invention after uviolizing, the pattern form of describing along the form of the difference with surface energy, image forms liquid self and in an organized way in the lower membrane that is used to form image, forms pattern, thereby can obtain the electrode of arbitrary graphic pattern shape.
Therefore, for the ultraviolet irradiation amount of lower membrane that is used to form image, need to form the amount that the contact angle of liquid fully changes with image and irradiate, but from energy efficiency with shorten the aspect such as time of manufacturing process, this irradiation dose is preferably 40J/cm 2below, 20J/cm more preferably 2below, most preferably be 10J/cm 2below.
In addition, being used to form the uviolizing portion of lower membrane of image and the image of irradiation portion not, to form the difference of contact angle of liquid larger, and it is easier that pattern forms, thereby electrode can be processed into complex pattern, fine pattern shape.In the case of the low solution of use surface tension, the difference of the contact angle of exposure portion and unexposed portion is preferably more than 5 °, more preferably more than 10 °, most preferably is more than 20 °.But, preferably consider that the coating process of image formation liquid, the surface tension of image formation liquid, the fineness of image, the flatness of film carry out suitable optimizing.
Based on same reason, form the contact angle of liquid for image, preferred ultraviolet ray not irradiation portion is more than 30 °, uviolizing portion is below 20 °.
Image formation liquid in the present invention refers to can be by after coating on substrate, make the solvent evaporation wherein comprising, the coating fluid using as functional film thus, for example can enumerate, by charge-transporting substance dissolves or be evenly dispersed at least one solvent and coating fluid.Herein, charge-transporting is identical with electroconductibility implication, refers to any in two charge-transportings of hole transport ability, electron-transporting, hole and electronics.
As above-mentioned charge-transporting material, can transporting holes or the electroconductibility of electronics as long as have, just do not limit especially.As the example, for example can enumerate the metal particles such as gold and silver, copper, aluminium, the inorganic materials such as carbon black, fullerene, carbon nanotube, organic pi-conjugated polymkeric substance such as Polythiophene, polyaniline, polypyrrole, poly-fluorenes and their derivative etc.
In addition,, in order to improve the charge transport ability of charge transport materials, can also form in liquid and to add following material as doping agent to image: (concrete example is Br for halogen, Lewis acid, protonic acid, transistion metal compound 2, I 2, Cl 2, FeCl 3, MoCl 5, BF 4, AsF 6, SO 4, HNO 4, H 2sO 4, polystyrolsulfon acid etc.) etc. electric charge acceptability material, or the electric charge such as basic metal, alkyl phosphate ion (concrete example is Li, Na, K, Cs, tetraethyl ammonium (テ ト ラ エ チ レ Application ア Application モ ニ ウ system), TBuA etc.) is supplied with property material.
Form the solvent of liquid as image, as long as can make above-mentioned charge-transporting material or doping agent dissolving or dispersed, just do not limit especially.From obtaining the such viewpoint of electrode image (pattern) accurately, the surface tension that preferred image forms liquid is 25mN/m～50mN/m.In the situation that surface tension is too low compared with above-mentioned scope, for not irradiation portion of ultraviolet ray, do not show fully large contact angle, in addition, in the situation that surface tension is too high compared with above-mentioned scope, because the contact angle of uviolizing portion increases, ultraviolet irradiation amount increases, therefore not preferred.
The solvent that forms liquid as image is not limited especially, can use the various organic solvents such as alcohols, ketone, ethers, ester class, aromatic hydrocarbon based, glycols.As alcohols, can enumerate methyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, isoamyl alcohol, octanol etc.As ketone, can enumerate acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone Pyranton etc.As ethers, can enumerate ether isopropyl ether, dioxane, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether etc.As ester class, can enumerate ethyl acetate, butylacetate, isobutyl acetate, pentyl acetate, cellosolve acetate, fatty acid methyl ester etc.As aromatic hydrocarbon based, can enumerate benzene,toluene,xylene, 1，3，5-trimethyl-benzene etc.
As aliphatic hydrocarbon, can enumerate normal hexane, isohexane, hexanaphthene, mineral spirits (ミ ネ ラ ル タ ー ペ Application), Skellysolve A etc.As glycols, can enumerate ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether etc.
In addition, from the viewpoint of the solvability excellence of organic system charge-transporting material, also preferred N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl-urea isopolarity solvent, but these polar solvents preferably use in to the little scope of the destruction of the lower membrane that is used to form image of the present invention.
In addition, also can make the king-sized solvent of the surface tension such as water, but preferred interpolation tensio-active agents etc. carry out adjustment sheet surface tension.
The concentration that image forms the charge-transporting material in liquid is preferably 0.01～30 quality %, and more preferably 0.1～10 quality %, most preferably is 1～5 quality %.
Form the concrete example of liquid as the image the present invention relates to, can enumerate the silver-colored particle dispersion liquids such as electric conductive polymer solution, De ー タ イ ト XA-9069 (Teng Cang changes into society's system), W4A (Sumitomo Electric Industries' system), NPS-J (Ha リ マ changes into society's system) such as Baytron (registered trademark) P (polyethylene dioxythiophene, バ イ エ Le society system) etc.
The electrode the present invention relates to is to form image by be coated with above-mentioned image formation liquid in the lower membrane that is used to form image of the present invention, then makes solvent evaporate to manufacture.As the method for evaporating of solvent, do not limit especially, can adopt hot plate, baking oven, under suitable atmosphere,, under the inert gas atmosphere such as atmosphere, nitrogen, wait and evaporate in a vacuum, obtain uniform film forming face.
The temperature that makes solvent evaporation is not limited especially, preferably at 40～250 ℃, carry out.From maintaining the viewpoint such as homogeneity that is used to form the lower membrane shape of image and realizes thickness, can carry out temperature variation more than 2 steps.
Form by this image the electrode that liquid is made and not only use as connection of electronic devices distribution each other, also as uses such as the electrodes of field-effect transistor, bipolar transistor, various diode, various sensor electron devices.
The electron device the present invention relates to has the electrode forming in the lower membrane that is used to form image of the invention described above, formed liquid making by image.
Below be presented at the example that uses the lower membrane that is used to form image of the present invention in organic FET element, but the invention is not restricted to this.
First, prepare to have in one side film forming the glass substrate of ITO electrode.Preferably adopt in advance washing composition, alcohol, pure water etc. to carry out liquid scrubbing substrate and purify, before by use, carry out the surface treatments such as ozonize, oxygen-Cement Composite Treated by Plasma.On the substrate with ITO electrode, form to contain according to the step of above-mentioned [manufacture method of film and cured film] and there is above-mentioned general formula (1) and the represented polyimide precursor of structural unit and/or the layer of polyimide of formula (1a).From taking into account driving voltage and electrical insulating property, the thickness of layer most preferably is 100nm～1000nm.Then, adopt the pattern-like ground irradiation ultraviolet radiations such as mask.
Next, adopted the image of the low surface tension solvent such as PGME to form liquid in the lower membrane surface coated that is used to form image.The image of coating forms liquid and is extended to rapidly wetting ability portion (uviolizing portion) stable to avoid the mode of hydrophobicity portion (ultraviolet ray is irradiation portion not), makes it dry, form patterning thus source electrode and drain electrode.The coating method that image forms liquid is method of spin coating, casting method etc., does not limit especially, preferably easily controls ink jet printing method, the spraying method of liquid measure.
Finally, by the organic semiconductor material such as pentacene, Polythiophene film forming is completed as the active coating of organic FET.The film of organic semiconductor material is not limited especially, can enumerate for example vacuum evaporation, solution is rotated to coating method, casting method, ink jet printing method, spraying method etc.
Thus, for the organic FET of manufacturing, can significantly reduce manufacturing process, can manufacture in addition than the more organic FET of jitty of mask evaporation method, even if therefore, in the case of adopting the organic semiconductor material of low mobility as active coating, also can discharge large electric current.In addition as the insulating film for organic transistor, can be the film that relative permittivity has more than 3.0 values.Because the lower membrane that is used to form image obtaining by method of the present invention also has excellent electrical insulating property, i.e. 3.0 such high relative dielectric constants, therefore also can be used as gate insulator (insulating film) and use, and can further simplify manufacturing process.
The sectional skeleton diagram that adopts aforesaid method to make the organic transistor obtaining is shown in Fig. 1.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the invention is not restricted to these embodiment.
[mensuration of number-average molecular weight and weight-average molecular weight]
The number-average molecular weight (hereinafter referred to as Mn) of the polyimide precursor obtaining according to following synthesis example and weight-average molecular weight (hereinafter referred to as Mw) are measured by GPC (normal temperature gel soaks into chromatogram), employing following apparatus and condition determination, calculate as polyoxyethylene glycol (or polyoxyethylene) scaled value.
GPC device: clear and electrician's (strain) Shodex processed (registered trademark) (GPC-101)
Post: clear and electrician's (strain) Shodex processed (registered trademark) (series connection of KD803, KD805)
Column temperature: 50 ℃
Elutriant: DMF
(as additive, 30 mmoles/L lithiumbromide-hydrate (LiBrH 2o), 30 mmoles/L phosphoric acid anhydrous crystal (o-phosphoric acid), 10ml/L tetrahydrofuran (THF) (THF))
Flow velocity: 1.0ml/ minute
Standard curve making standard substance:
East ソ ー (strain) TSK standard processed polyoxyethylene (molecular weight: 900,000,150,000,100,000,30,000)
Port リ マ ー ラ ボ ラ ト リ ー society polyoxyethylene glycol processed (molecular weight: approximately 12,000,4,000,1,000).
[mensuration of thickness]
The thickness of polyimide film is obtained as follows: peel off a part of film with cutters, adopting full-automatic fine shape measuring machine (ET4000A, (strain) little slope institute system) is that 10 μ N, sweep velocity are under 0.05mm/ second, to measure its section of difference to obtain in mensuration power.
[ultraviolet irradiation]
Using high pressure mercury vapour lamp as light source, be situated between by the bandpass filter that sees through near light wavelength 254nm by uviolizing on polyimide film.
It should be noted that, the ultraviolet illumination on polyimide film is multiplied by result that the time shutter the obtains exposure (J/cm on polyimide film 2) calculate.
The detector that the Deep UV that above-mentioned ultraviolet illumination has wavelength 253.7nm peak sensitivity in the upper installation of luxmeter (MODEL306 processed of OAI society) uses is measured, and the illumination of gained is 45～50mW/cm 2.
[mensuration of contact angle]
The mensuration of contact angle is to measure at the lower full-automatic contact angle meter CA-W of use of constant-temperature constant-humidity environment (25 ℃ ± 2 ℃, 50%RH ± 5%) (consonance interface science (strain) system).
It should be noted that, the contact angle of propylene glycol monomethyl ether (PGME) is to be 3.0～3.5 μ l in liquid measure, after contact liq static 5 seconds, then measure, in addition, the contact angle of pure water is to be 3 μ l in liquid measure, after contact liq static 5 seconds, then measure.
< synthesis example 1>
The polymerization of polyimide precursor (PI-1)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 50mL, add 1.8823g (0.0094 mole) 4, 4 '-diaminodiphenyl oxide (hereinafter referred to as ODA) and 0.3579g (0.0006 mole) 3, 5-diaminobenzoic acid 11-(perfluor-n-hexyl)-n-undecane base ester (hereinafter referred to as APC11-6F), this mixture is dissolved in 23.58g METHYLPYRROLIDONE (hereinafter referred to as NMP), then add 1.9219g (0.0098 mole) 1, 2, 3, 4-tetramethylene tetracarboxylic acid dianhydride (hereinafter referred to as CBDA), it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, dilute with NMP again, obtain thus 6 quality % solution of polyimide precursor (PI-1).
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-1) of gained are respectively Mn=35, and 200, Mw=83,600.
< synthesis example 2>
The polymerization of polyimide (PI-2)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 3.3501g (0.0167325 mole) ODA, 1.6164g (0.004462 mole) 2, two (3-amino-4-aminomethyl phenyl) HFC-236fa (hereinafter referred to as AMF) of 2-, 0.6965g (0.0011155 mole) APC11-6F, this mixture is dissolved in 49.44gNMP, then add 6.6981g (0.02231 mole) 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride (hereinafter referred to as TDA) stirs it and within 24 hours, carries out polyreaction at 50 ℃.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 60g, add 22.1g diacetyl oxide, the 10.3g pyridine as imidization catalyst, it is reacted 3 hours at 50 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, is dried, thereby obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.Make this powder dissolution of 4g in the mixed solvent of 30g gamma-butyrolactone and 6g dipropylene glycol monomethyl ether, thereby obtain 10 quality % solution of polyimide (PI-2).
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-2) of gained are respectively Mn=13, and 900, Mw=28,400.
< synthesis example 3>
The polymerization of polyimide (PI-3)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 50mL, add 2.7769g (0.0095 mole) 1, two (4-amino-benzene oxygen) benzene (hereinafter referred to as DA-4P) of 3-, 0.3122g (0.0005 mole) APC11-6F, it is dissolved in 21.96g NMP, then add 2.402g (0.0099 mole) two ring [3.3.0]-octane-2,4,6,8-tetracarboxylic acid dianhydride (hereinafter referred to as BODA) stirs it and within 24 hours, carries out polyreaction at 40 ℃.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 23g, add 8.5g diacetyl oxide, the 3.9g pyridine as imidization catalyst, it is reacted 3 hours at 100 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, is dried, thereby obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.Make this powder dissolution of 3g in the mixed solvent of 22.5g gamma-butyrolactone and 4.5g dipropylene glycol monomethyl ether, thereby obtain 10 quality % solution of polyimide (PI-3).
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-3) of gained are respectively Mn=19,300, Mw=50,300.
< synthesis example 4>
The polymerization of polyimide precursor (PI-4)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 2.8234g (0.0141 mole) ODA and 0.5620g (0.0009 mole) APC11-6F, it is dissolved in 36.97g NMP, then add 3.1084g (0.01425 mole) 1,2,4,5-pyromellitic acid dianhydride (hereinafter referred to as PMDA), it is stirred at 23 ℃ and within 5 hours, carry out polyreaction, with NMP dilution, obtain thus 8 quality % solution of polyimide precursor (PI-4) again.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-4) of gained are respectively Mn=15,500, Mw=35,000.
< is synthesis example 1> relatively
The polymerization of polyimide precursor (PI-5)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 200mL, add 15.065g (0.040 mole) 1-octadecane oxygen base-2,4-diaminobenzene (hereinafter referred to as APC18), it is dissolved in 127.6g NMP, then add 7.45g (0.038 mole) CBDA, it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, then with NMP dilution, obtain thus 2 quality % solution of polyamic acid (PI-5).
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyamic acid (PI-5) of gained are respectively Mn=16,000, Mw=48,000.
< is synthesis example 2> relatively
The polymerization of polyimide precursor (PI-6)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 50mL, add 2.9856g (0.01491 mole) ODA and 0.0562g (0.00009 mole) APC11-6F, it is dissolved in 24.93g NMP, then add 2.7946g (0.01425 mole) CBDA, it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, with NMP dilution, obtain thus 6 quality % solution of polyimide precursor (PI-6) again.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-6) of gained are respectively Mn=14,200, Mw=28,500.
Below, the tetracarboxylic dianhydride who uses in demonstration synthesis example and comparison synthesis example and the table look-up of diamines.
The tetracarboxylic dianhydride and the diamines that in (table 1) synthesis example and relatively synthesis example, use
Figure BDA0000459641930000301
※ 1: the molar fraction of the each tetracarboxylic dianhydride in the total tetracarboxylic dianhydride of numeral in table, and the molar fraction of each diamines in total diamines.
< embodiment 1: ultraviolet sensory characteristic (contact angle of the PGME) > of the polyimide film being formed by PI-1
On the glass substrate with ITO (2.5cm × 2.5cm, thickness is 0.7mm), use the solution that drips the PI-1 of preparation in synthesis example 1 with the syringe of 0.2 μ m millipore filter, and be coated with by method of spin coating.Subsequently under atmosphere, carry out heat treated 5 minutes with the hot plates of 80 ℃, make organic solvent volatilization, then with the hot plate baking of 180 ℃ 30 minutes, thereby acquisition thickness is about the polyimide film of 400nm.Measure the contact angle of the PGME of this polyimide film.
With 6J/cm 2irradiation dose to adopting the polyimide film irradiation ultraviolet radiation of same step gained, measure the contact angle of PGME.
The measurement result of the contact angle of PGME is shown in table 2.
< embodiment 2～embodiment 4, comparative example 1 and comparative example 2: ultraviolet sensory characteristic (contact angle of the PGME) > of the polyimide film being formed by PI-2～PI-6
Adopt synthesis example 2～synthesis example 4, relatively synthesis example 1 and the solution of the PI-2～PI-6 of preparation in synthesis example 2 relatively, adopt step similarly to Example 1 to manufacture polyimide film, measure respectively not irradiation ultraviolet radiation, irradiate 6J/cm 2the contact angle of PGME after ultraviolet ray.
The measurement result of the contact angle of PGME is shown in table 2.
The contact angle of PGME before and after (table 2) uviolizing
Figure BDA0000459641930000311
※ 1: the molar fraction of the each amine in the total diamines of numeral in bracket.
As shown in Table 2 above, with the polyimide precursor being related to by the lower membrane composition that is used to form image of the present invention or polyimide and embodiment 1～embodiment 4 corresponding to the cured film obtaining shows lyophobicity, the variable quantity of the hydrophilic and hydrophobic that uviolizing causes is 8～21 °, thereby can obtain the contact angle difference (more than 5 °) that can form image.
On the other hand, the polyimide film (comparative example 1) being obtained by PI-5 does not show liquid repellency, even and if can not change by irradiation ultraviolet radiation wetting ability yet.Because the contact angle after uviolizing increases slightly, therefore can not form image.
In addition,, although the polyimide film being obtained by PI-6 (comparative example 2) shows liquid repellency, the variable quantity of the hydrophilic and hydrophobic that uviolizing causes is less, is 3.7 °, therefore can not obtain the contact angle difference that can form image.
< embodiment 5～8: ultraviolet sensory characteristic (contact angle of the water) > of the polyimide film being formed by PI-1～PI-4
Adopt the solution of the PI-1～PI-4 of preparation in above-mentioned synthesis example 1～synthesis example 4, adopt step similarly to Example 1 to manufacture polyimide film, measure respectively not irradiation ultraviolet radiation, irradiation 40J/cm 2the contact angle of the water after ultraviolet ray.
The measurement result of the contact angle of water is shown in table 3.
The contact angle of the water before and after (table 3) uviolizing
Figure BDA0000459641930000321
※ 1: the molar fraction of the each amine in the total diamines of numeral in bracket.
As shown in table 3, with the polyimide precursor being related to by the lower membrane composition that is used to form image of the present invention or polyimide and embodiment 5～embodiment 8 corresponding to the cured film obtaining can obtain large contact angle difference by uviolizing.
Show, the lower membrane that is used to form image of the present invention can make various capillary images form liquid and form pattern.
< embodiment 9: by the relative permittivity > of the polyimide film of PI-2 film forming
On the glass substrate with ITO (2.5cm × 2.5cm, thickness is 0.7mm), use the solution that drips the PI-2 of preparation in synthesis example 2 with the syringe of 0.2 μ m millipore filter, and be coated with by method of spin coating.Subsequently, under atmosphere, heat 5 minutes so that organic solvent volatilization with the hot plate of 80 ℃, then with the hot plate baking of 180 ℃ 60 minutes, thereby acquisition thickness is about the polyimide film of 400nm.
Next, in order to obtain the good contact of probe of ITO electrode and determinator, wipe a part of polyimide film off ITO is exposed, then adopt vacuum deposition apparatus is the aluminium electrode that 1.0mm, thickness are 100nm with ITO superimposed layer diameter on polyimide film.Vacuum evaporation condition is now, room temperature, and vacuum tightness is 3 × 10 -3below Pa, aluminium-vapour deposition speed is below 0.3nm/ second.Thus, at the electrode of formation up and down of polyimide film, thereby manufacture the sample that is used for the relative permittivity of evaluating polyimide film.
This relative permittivity that is used for the sample of the relative permittivity of evaluating polyimide film is 3.0, although this shows that water-repellancy is higher, but can guarantee more than 3.0 relative permittivity using as the gate insulating film for organic transistor, and show excellent characteristic.
In addition, the Leakage Current density in the time applying 1MV/cm electric field is 2 × 10 -10a/cm 2, this confirms as for the gate insulating film of organic transistor, insulativity is no problem aspect practical.
It should be noted that, in the present embodiment, the relative permittivity of polyimide film adopts peace rattan electric (strain) AG-4311B processed, mensuration electrostatic capacity and obtaining.Electrostatic capacity is to measure and obtain under 1KHz in nitrogen atmosphere, in frequency.In addition, the mensuration of the Leakage Current density of polyimide film has been used the ア ジ レ Application ト テ Network ノ ロ ジ ー HP4156C processed of society.
< comparative example 3: by the relative permittivity > of the polyimide film of PI-5 film forming
Adopt the solution that compares the PI-5 of preparation in synthesis example 1, the storing temperature that makes in a vacuum film is 250 ℃, toasts 60 minutes, and making thickness is 270nm, in addition, adopt method similarly to Example 9 to evaluate the relative permittivity by the polyimide film of PI-5 film forming.
By the polyimide film of PI-5 film forming, Leakage Current density is 1 × 10 -10a/cm 2below, but relative permittivity is 2.7.In the time using as gate insulating film, relative permittivity is lower, even if for example obtain the performance that forms lower membrane as image, can not use as gate insulating film.
< synthesis example 5>
The polymerization of polyimide precursor (PI-7)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 1.7621g (0.0088 mole) ODA and 0.7158g (0.0012 mole) APC11-6F, it is dissolved in 24.93g NMP, then add 1.9219g (0.0098 mole) CBDA, it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, with NMP dilution, obtain thus 6 quality % solution of polyimide precursor (PI-7) again.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-7) of gained are respectively Mn=29,630, Mw=67,400.
< synthesis example 6>
The polymerization of polyimide (PI-8)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 3.4366g (0.01716 mole) ODA, 1.6151g (0.004458 mole) AMF and 0.4176g (0.000669 mole) APC11-6F, it is dissolved in 48.65g NMP, then add 6.6927g (0.02229 mole) TDA, it is stirred at 50 ℃ and within 24 hours, carry out polyreaction.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 148g, add 22.2g diacetyl oxide, the 10.3g pyridine as imidization catalyst, it is reacted 3 hours at 50 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, is dried, thereby obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.By this powder dissolution of 4g in the mixed solvent of 30g gamma-butyrolactone and 6g dipropylene glycol monomethyl ether, thereby obtain polyimide (PI-8) 10 quality % solution.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-8) of gained are respectively Mn=15,300, Mw=31,500.
< synthesis example 7>
The polymerization of polyimide precursor (PI-9)
Under stream of nitrogen gas, add 3.5683g (0.01782 mole) ODA, 0.1113g (0.00018 mole) 1-(4-perfluoro capryl) phenoxy group-2 to 4 mouthfuls of flasks of 100mL, 4-diaminobenzene (hereinafter referred to as DA-1), it is dissolved in 27.99g NMP, then add 3.3182g (0.01692 mole) CBDA, it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, with NMP dilution, obtain thus 8 quality % solution of polyimide precursor (PI-9) again.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-9) of gained are respectively Mn=31,500, Mw=67,200.
Figure BDA0000459641930000341
< synthesis example 8>
The polymerization of polyimide precursor (PI-10)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 1.9624g (0.0098 mole) ODA, 0.1237g (0.0002 mole) DA-1, it is dissolved in 15.72g NMP, then add 1.8434g (0.0094 mole) CBDA, it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, with NMP dilution, obtain thus 8 quality % solution of polyimide precursor (PI-10) again.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-10) of gained are respectively Mn=31,200, Mw=68,100.
< synthesis example 9>
The polymerization of polyimide (PI-11)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 5.887g (0.0294 mole) ODA, 0.371g (0.0006 mole) DA-1, it is dissolved in 60.88g NMP, then add 8.9631g (0.03 mole) TDA, it is stirred at 50 ℃ and within 24 hours, carry out polyreaction.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 170g, add 27.8g diacetyl oxide, the 12.9g pyridine as imidization catalyst, it is reacted 3 hours at 50 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, is dried, thereby obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.Make this powder dissolution of 4g in the mixed solvent of 30g gamma-butyrolactone and 6g dipropylene glycol monomethyl ether, thereby obtain 10 quality % solution of polyimide (PI-11).
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-11) of gained are respectively Mn=30,470, Mw=66,900.
< synthesis example 10>
The polymerization of polyimide (PI-12)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 8.0458g (0.0196 mole) DA-3,0.2473g (0.0004 mole) DA-1, it is dissolved in 56.7g NMP, then add 5.8853g (0.0196 mole) TDA, it is stirred at 50 ℃ and within 24 hours, carry out polyreaction.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 177g, add 19.3g diacetyl oxide, the 8.9g pyridine as imidization catalyst, it is reacted 3 hours at 50 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, is dried, thereby obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.By this powder dissolution of 4g in the mixed solvent of 52.67g gamma-butyrolactone and 10g dipropylene glycol monomethyl ether, thereby obtain polyimide (PI-12) 6 quality % solution.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-12) of gained are respectively Mn=19,700, Mw=47,960.
< synthesis example 11>
The polymerization of polyimide (PI-13)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 100mL, add 5.1764g (0.01261 mole) DA-3,0.2411g (0.00039 mole) DA-1, it is dissolved in 36.77g NMP, then add 5.1764g (0.012571 mole) TDA, it is stirred at 50 ℃ and within 24 hours, carry out polyreaction.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 130g, add 11.6g diacetyl oxide, the 5.4g pyridine as imidization catalyst, it is reacted 3 hours at 50 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, dry, thus obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.By this powder dissolution of 4g in the mixed solvent of 52.67g gamma-butyrolactone and 10g dipropylene glycol monomethyl ether, thereby obtain polyimide (PI-13) 6 quality % solution.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-13) of gained are respectively Mn=20,970, Mw=51,220.
< is synthesis example 3> relatively
The polymerization of polyimide precursor (PI-14)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 50mL, add 1.0673g (0.0026 mole) DA-3 and 0.8656g (0.0014 mole) DA-1, it is dissolved in 15.31g NMP, then add 0.7688g (0.00392 mole) CBDA, it is stirred at 23 ℃ and within 12 hours, carry out polyreaction, with NMP dilution, obtain thus 6 quality % solution of polyimide precursor (PI-14) again.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide precursor (PI-14) of gained are respectively Mn=20,130, Mw=48,280.
Below show synthesis example 5～synthesis example 11 and compare the tetracarboxylic dianhydride of use in synthesis example 3 and the table look-up of diamines.Numeral in table is the molar ratio with respect to 100 o'clock by the addition of each tetracarboxylic dianhydride and diamines.
The tetracarboxylic dianhydride who uses in (table 4) synthesis example and comparative example and diamines
Figure BDA0000459641930000371
※ 1: the molar fraction of the each tetracarboxylic dianhydride in the total tetracarboxylic dianhydride of numeral in table, and the molar fraction of each diamines in total diamines.
< synthesis example 12>
The polymerization of polyimide (PI-15)
Under stream of nitrogen gas, in 4 mouthfuls of flasks of 200mL, add 4.86g (0.045 mole) Ursol D, 1.74g (0.005 mole) 4-n-Hexadecane Oxy-1,3-diaminobenzene, it is dissolved in 122.5gNMP, add 15.01g (0.05 mole) TDA, it is at room temperature stirred and within 10 hours, carries out polyreaction.The solution of the polyamic acid of gained is diluted to 8 quality % with NMP.
In this solution of 50g, add 10.8g diacetyl oxide, the 5.0g pyridine as imidization catalyst, it is reacted 3 hours at 50 ℃, thereby obtain polyimide solution.This solution is dropped in a large amount of methyl alcohol, the white precipitate of gained is filtered, is dried, thereby obtain white polyimide powder.Pass through 1h-NMR confirm this polyimide powder more than 90% by imidization.By this powder dissolution of 4g in the mixed solvent of 52.67g gamma-butyrolactone and 10g dipropylene glycol monomethyl ether, thereby obtain polyimide (PI-15) 6 quality % solution.
Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polyimide (PI-15) of gained are respectively Mn=18,000, Mw=54,000.
< embodiment 10: the observation > that the wettability of the silver-colored particle dispersion liquid (W4A) of the polyimide film being formed by PI-1 changes
On the glass substrate with ITO (2.5cm × 2.5cm, thickness is 0.7mm), use the solution that drips the PI-1 of preparation in synthesis example 1 with the syringe of 0.2 μ m millipore filter, be coated with by method of spin coating.Subsequently, under atmosphere, carry out heat treated 5 minutes with the hot plates of 80 ℃, make organic solvent volatilization, then with the hot plate baking of 180 ℃ 30 minutes, thereby acquisition thickness is about the polyimide film of 400nm.On this polyimide film, drip 3 μ l silver particle dispersion liquids (goods name W4A, Sumitomo Electric Industries' system), result is that polyimide film shows lyophobicity to silver-colored particle dispersion liquid.
To adopting the polyimide film of same step acquisition with 6J/cm 2irradiation dose irradiation ultraviolet radiation, on this polyimide film, drip 3 μ l silver particle dispersion liquids, result is that polyimide film shows lyophily to silver-colored particle dispersion liquid.
The polyimide film being obtained by PI-1 can be controlled the lyophobicity lyophily of the silver-colored particle dispersion liquid that uviolizing causes.
< embodiment 11～embodiment 19, comparative example 4～comparative example 6: the observation > that the wettability of the polyimide film being formed by PI-1～PI-3, PI-5～PI-13 changes
Adopt the solution of PI-2, PI-3, PI-5～PI-14, adopt step similarly to Example 1 to manufacture polyimide film, observe not irradiation ultraviolet radiation, irradiation 6J/cm 2the lyophobicity lyophily of polyimide film after ultraviolet ray to silver-colored particle dispersion liquid.The results are shown in table 5.
(table 5) changes the wettability of silver-colored particle dispersion liquid (W4A)
NO. Use PI Acid Diamines The variation of wettability
Embodiment
10 PI-1 CBDA ODA(94)，APC11-6F(6) Have
Embodiment 11 PI-2 TDA ODA(75)，AMF(20)，APC11-6F(5) Have
Embodiment 12 PI-3 BODA DA-4P(95)，APC11-6F(5) Have
Comparative example 4 PI-5 CBDA APC18(100) Nothing
Comparative example 5 PI-6 CBDA ODA(99.4)，APC11-6F(0.6) Nothing
Embodiment 13 PI-7 CBDA ODA(88)，APC11-6F(12) Have
Embodiment 14 PI-8 TDA ODA(77)，AMF(20)，APC11-6F(3) Have
Embodiment 15 PI-9 CBDA ODA(99)，DA-1(1) Have
Embodiment 16 PI-10 CBDA ODA(98)，DA-1(2) Have
Embodiment 17 PI-11 TDA ODA(98)，DA-1(2) Have
Embodiment 18 PI-12 TDA DA-3(98).DA-1(2) Have
Embodiment 19 PI-13 TDA DA-3(97)，DA-1(3) Have
※ 1: the molar fraction of the each amine in the total diamines of numeral in bracket.
※ 2: when irradiating 6J/cm to polyimide film 2when ultraviolet ray, the polyimide film that becomes lyophily from lyophobicity has wettability to change, and polyimide film in addition changes without wettability.
As shown in Table 5 above, with the polyimide precursor being related to by the lower membrane composition that is used to form image of the present invention or polyimide and embodiment 10～embodiment 19 corresponding to the cured film obtaining exist by uviolizing and make the wettability of silver-colored particle dispersion liquid change.Can utilize wettability difference to change to form image.
On the other hand, by PI-5, PI-6 obtain polyimide film (comparative example 4, comparative example 5) even irradiation ultraviolet radiation, wettability also can not change.
[about polymer blend]
The formulation example 1 of < composition: the preparation > that is used to form the lower membrane composition of image
The solution 1.5g of 6 % by weight of the polyimide (PI-12) of preparation in the solution 8.5g of 6 % by weight of the polyimide (PI-15) of preparation in synthesis example 12 and synthesis example 10 is mixed, at room temperature stir 6 hours, thereby obtain composition A.
The formulation example 2 of < composition: the preparation > that is used to form the lower membrane composition of image
In synthesis example 12, the solution 9g of 6 % by weight of the polyimide (PI-15) of preparation mixes with the solution 1g of 6 % by weight of the polyimide (PI-13) of preparation in synthesis example 11, at room temperature stirs 6 hours, thereby obtains composition B.
The formulation example 3 of < composition: the preparation > that is used to form the lower membrane composition of image
The solution 8.5g of 6 % by weight of the polyimide (PI-15) of preparation in synthesis example 12 is mixed with the solution 1.5g of 6 % by weight of the polyimide (PI-13) of preparation in synthesis example 11, at room temperature stir 6 hours, thereby obtain composition C.
The formulation example 4 of < composition: the preparation > that is used to form the lower membrane composition of image
In synthesis example 12, the solution 8g of 6 % by weight of the polyimide (PI-15) of preparation mixes with the solution 2g of 6 % by weight of the polyimide (PI-13) of preparation in synthesis example 11, at room temperature stirs 6 hours, thereby obtains composition D.
The formulation example 5 of < composition: the preparation > that is used to form the lower membrane composition of image
The solution 7.5g of 6 % by weight of the polyimide (PI-15) of preparation in synthesis example 12 is mixed with the solution 2.5g of 6 % by weight of the polyimide (PI-13) of preparation in synthesis example 11, at room temperature stir 6 hours, thereby obtain composition E.
The formulation example 6 of < composition: the preparation > that is used to form the lower membrane composition of image
The solution 7g of 6 % by weight of the polyimide (PI-15) of preparation in synthesis example 12 is mixed with the solution 3g of 6 % by weight of the polyimide (PI-13) of preparation in synthesis example 11, at room temperature stir 6 hours, thereby obtain composition F.
The formulation example 7 of < composition: the preparation > that is used to form the lower membrane composition of image
The solution 9g of 6 % by weight of the polyimide (PI-15) of preparation in synthesis example 12 is mixed with the solution 1g of 6 % by weight of the polyimide (PI-14) of preparation in comparative example synthesis example 3, at room temperature stir 6 hours, thereby obtain composition G.
< embodiment 20: the pattern formative > of electrode
Use the formulation example 1 that drips composition with the syringe of 0.2 μ m millipore filter on the glass substrate with ITO (2.5cm × 2.5cm, thickness is 0.7mm) in, the composition A of preparation, is coated with by method of spin coating.Subsequently, under atmosphere, by the hot plate heat treated of 80 ℃ 5 minutes, make organic solvent volatilization, then with the hot plate baking of 180 ℃ 30 minutes, thereby acquisition thickness is about the polyimide film of 450nm.By photomask, this polyimide film is irradiated to 6J/cm with pattern-like 2ultraviolet ray.Next, the silver-colored particle dispersion liquid of denier is dropped to uviolizing portion, result is that the uviolizing portion of polyimide film shows lyophily.Subsequently, by the hot plate bakings of 180 ℃ 60 minutes, the silver electrode that formation thickness is 50nm.
The microphotograph of this silver electrode is shown in Fig. 2.
< embodiment 21～embodiment 27: the pattern formative > of electrode
Except adopting the solution of composition B～composition F and PI-12～PI-13, adopt step similarly to Example 20 to carry out film forming polyimide film, adopt silver-colored particle dispersion liquid to form silver electrode.Can all on polyimide film, form the silver electrode that electrode space is 10 μ m.
< comparative example 7>
Except adopting the solution of composition G, attempt adopting step similarly to Example 20 to carry out film forming polyimide film, adopt silver-colored particle dispersion liquid to form silver electrode.In the polyimide film obtaining at the solution by composition G, uviolizing portion shows hydrophobicity, can not form target silver electrode (Fig. 3).
< comparative example 8～comparative example 9>
Except having adopted the solution of PI-5～PI-6, attempt adopting step similarly to Example 20 to carry out film forming polyimide film, adopt silver-colored particle dispersion liquid to form silver electrode.In the polyimide film obtaining at solution by PI-5～PI-6, no matter whether irradiation ultraviolet radiation, all can not form electrode, can not form target silver electrode.
The pattern formative of the silver-colored particle dispersion liquid of table 6 polyimide film of the present invention
? ? Blending is than (quality %) Electrode pattern
Embodiment
20 Composition A PI-15/PI-12(15) Can form
Embodiment 21 Composition B PI-15/PI-13(10) Can form
Embodiment 22 Composition C PI-15/PI-13(15) Can form
Embodiment 23 Composition D PI-15/PI-13(20) Can form
Embodiment 24 Composition E PI-15/PI-13(25) Can form
Embodiment 25 Composition F PI-15/PI-13(30) Can form
Embodiment 26 PI-12 PI-12(100) Can form
Embodiment 27 PI-13 PI-13(100) Can form
Comparative example 7 Composition G PI-15/PI-14(10) Cannot form
Comparative example 8 PI-5 PI-5(100) Cannot form
Comparative example 9 PI-6 PI-6(100) Cannot form
< embodiment 28: than the mensuration > of the relative permittivity of resistance
On the glass substrate with ITO (2.5cm × 2.5cm, thickness is 0.7mm), use the composition A that drips preparation in composition liquid formulation example 1 with the syringe of 0.2 μ m millipore filter, be coated with by method of spin coating.Subsequently, in atmosphere, by the hot plate heat treated of 80 ℃ 5 minutes, make organic solvent volatilization.Then, with the hot plate bakings of 180 ℃ 30 minutes, thereby obtain the polyimide film that thickness is about 450nm.
Then, adopt vacuum deposition apparatus, be the aluminium electrode that 1.0mm～2.0mm, thickness are 100nm at above-mentioned polyimide film superimposed layer diameter, thereby be manufactured on the polyimide film insulativity sample for evaluation that has electrode setting up and down of polyimide film.It should be noted that, vacuum evaporation condition is now, room temperature, and vacuum tightness is 3 × 10 -3below Pa, the evaporation rate of aluminium is below 0.5nm/ second.
Adopt this sample, in the air atmosphere that is 45% ± 5% in room temperature, humidity, measure electric current. voltage characteristic.For voltage, be arranged to from the every step 2V of 0V to 80V, hold-time be 3 seconds, apply positive voltage to aluminium electrode side, the current value while being 1MV/cm by electric field is obtained and is compared resistance.Measurement result than resistance and relative permittivity is shown in table 7.
< embodiment 29～embodiment 35>
Except adopting the solution of composition B～composition F and PI-12～PI-13, adopt step similarly to Example 28 to carry out film forming polyimide film, measure than resistance and relative permittivity.
The results are shown in table 7.
Ratio resistance and the relative permittivity of table 7 polyimide film of the present invention
? ? Blending is than (quality %) Than resistance (Ω cm) Relative permittivity
Embodiment 28 Composition A PI-15/PI-12(15) >10 15 3.2
Embodiment 29 Composition B PI-15/PI-13(10) >10 15 3.2
Embodiment 30 Composition C PI-15/PI-13(15) >10 15 3.2
Embodiment 31 Composition D PI-15/PI-13(20) >10 15 3.2
Embodiment 32 Composition E PI-15/PI-13(25) >10 15 3.1
Embodiment 33 Composition F PI-15/PI-13(30) >10 15 3.1
Embodiment 34 PI-12 PI-12(100) >10 15 3
Embodiment 35 PI-13 PI-13(100) >10 15 3
< embodiment 36: organic crystal pipe manufacturer >
In the silver electrode obtaining in embodiment 20, to gather (3-hexyl thiophene-2,5-bis-bases) (derive from メ Le Network (strain), later referred to as P3HT) be dissolved in the coating solution with preparation P3HT in dimethylbenzene with the concentration of 2 quality %, be to adopt method of spin coating to be coated on above-mentioned polyimide film this coating solution under the nitrogen atmosphere below 0.5ppm in oxygen concentration.
Subsequently, for solvent is volatilized completely, under vacuum state at 100 ℃ heat treated 60 minutes, form semiconductor layer, thereby completed OTFT.
Evaluate the electrical characteristic of the OTFT of acquisition described above with respect to the variation of grid voltage by measuring drain current.
In detail, source drain voltage (V d) be-40V grid voltage (V g) be+30V～-30V, changing with every step 2V, record is until electric current is fully stablized the measured value of the value of sustaining voltage after 1 second as drain current.It should be noted that, in mensuration, adopt analyzing parameters of semiconductor instrument HP4156C (ア ジ レ Application ト テ Network ノ ロ ジ mono-(strain) system).
In the time applying grid voltage to negative pole, observe increasing considerably of drain current, confirm that P3HT is as p-type semi-conductor work (Fig. 4).
Then, the drain current when measuring grid voltage (VG) and changing with every step 10V from+20V to-30V and the relation of drain voltage, confirmed organic transistor normally work (Fig. 5).
Generally speaking, the drain current I under state of saturation dcan represent with following formula.That is to say, organic semi-conductor mobility [mu] can be by with drain current I dthe square root of absolute value be the longitudinal axis, with grid voltage V gthe slope of the figure while drawing for transverse axis is obtained.
I D=WCμ(V G-V T) 2/2L
In above-mentioned formula, W is transistorized passage width, and L is transistorized passage length, and C is the electrostatic capacity of gate insulating film, V tbe transistorized threshold voltage, μ is mobility.Calculate the mobility [mu] of P3HT based on this formula, result is 2 × 10 -3cm 2/ Vs.In addition, threshold voltage is 16V, and the ratio (on/Off ratio) of open state and closing condition is 10 2the order of magnitude (table 8).
It should be noted that, in order to eliminate the humidity of periphery and the impact of active substance, OTFT electrical characteristic are measured as follows: after element completes, move to rapidly that in vacuum, (vacuum tightness is 5 × 10 -2pa is following), place about 30 minutes, be then 5 × l0 in vacuum tightness -2pa preserves and measures below.
< embodiment 37: organic transistor >
Except adopt the silver electrode obtaining in embodiment 2l, adopt the step same with embodiment 36 to manufacture organic transistor.
< embodiment 38: organic transistor >
The silver electrode obtaining in adopting embodiment 27, adopt the step same with embodiment 36 to manufacture organic transistor.
The characteristic of the organic transistor of manufacturing in table 8 embodiment 36～embodiment 38
? ? Blending is than (quality %) Mobility (cm 2/Vs) On/Off ratio Vt(V)
Embodiment 36 Composition A PI-15/PI-12(15) 2×10 -3 >10 2 16
Embodiment 37 Composition B PI-15/PI-13(10) 2×10 -3 >10 2 15
Embodiment 38 PI-13 PI-13(100) 3×10 —3 >10 2 19
Demonstrate polyimide of the present invention and can utilize the pattern of the electrode of close and distant water difference to form (composition), can manufacture the organic transistor that passage length is 10 μ m.
In addition, show 10 l5relative permittivity more than high-insulativity more than Ω cm and 3.0, and demonstrate and not only have as being used to form the lower membrane of image but also thering is the high-performance as the effective gate insulating film of organic crystal.
From above result, by the cured film that is used to form the lower membrane composition of image and obtain of the present invention that comprises the polyimide precursor that contains fluoroalkyl and/or the polyimide being obtained by this polyimide precursor, because hydrophobicity is high, relative permittivity is higher, it is also useful therefore demonstrating in the situation that using as gate insulating film.
Accompanying drawing explanation
Fig. 1 shows to have the sectional skeleton diagram of image shape of the present invention with the organic transistor structure of lower membrane.
Fig. 2 is that the pattern of the silver-colored particle dispersion liquid of acquisition in embodiment 20 forms example.
Fig. 3 is that the pattern of the silver-colored particle dispersion liquid of acquisition in comparative example 7 forms example.
Fig. 4 is presented in embodiment 36, the figure of the drain current (Drain Current) of the organic transistor of the gate insulating film of holding concurrently the polyimide film being obtained by composition A as the lower floor that is used to form image and the relation of grid voltage (Gate Voltage).
Fig. 5 is presented in embodiment 36, the figure of the drain current (Drain Current) of the organic transistor of the gate insulating film of holding concurrently the polyimide film being obtained by composition A as the lower floor that is used to form image and the relation of drain voltage (Drain Voltage).
Description of reference numerals
1 substrate
2 gate electrodes
3 lower membrane that the are used to form electrode gate insulating film of holding concurrently
4 source electrodes, drain electrode
5 semiconductor layers

Claims (5)

1. the effective gate insulating film of organic crystal, that the lower membrane composition that is used to form image obtains, the described lower membrane composition that is used to form image comprises and is selected from that polyimide precursor and this polyimide precursor carry out dehydration closed-loop and at least one compound in the polyimide that obtains, described polyimide precursor comprises following formula (1) and the represented structural unit of formula (1a)
In above formula, A represents 4 valency organic groups, B 1represent at least a kind of divalent organic group that following formula (2) is represented, B 2represent divalent organic group, R 1, R 2, R 1a, R 2arepresent independently of one another hydrogen atom or 1 valency organic group, n is the total mole number of the represented structural unit of formula (1), m is the total mole number of the represented structural unit of formula (1a), and n and m represent respectively positive integer and meet 0.01≤n/ (n+m)≤0.3
Figure FDA0000459641920000012
In above formula, X 1represent singly-bound ,-O-,-COO-,-OCO-,-CONH-,-CH 2o-, X 2represent the divalent organic group that carbonatoms is 3～18, R 3represent the perfluoroalkyl that carbonatoms is 2～12.
2. the effective gate insulating film of organic crystal according to claim 1, in above-mentioned formula (1a), B 2at least one the group being selected from following formula (3)～(5),
Figure FDA0000459641920000013
In above formula, Y 1represent independently of one another the alkylenedioxy group can with branched structure that the alkylidene group can with branched structure that singly-bound, ehter bond, ester bond, thioether bond, amido linkage, carbonatoms are 1～3 or carbonatoms are 1～3, Y 2represent singly-bound, ehter bond, ester bond, thioether bond, amido linkage, R 4represent independently of one another hydrogen atom, methyl, ethyl, trifluoromethyl, R 5represent hydrogen atom, methyl, trifluoromethyl, R 6represent methylene radical, ethylidene, j represents 0 or 1 independently of one another.
3. the effective gate insulating film of organic crystal according to claim 1 and 2, in above-mentioned formula (1) and formula (1a), 4 represented valency organic groups of A are at least one groups that are selected from following formula (6)～(11)
Figure FDA0000459641920000021
In above formula, R 7, R 8, R 9, R 10represent that independently of one another hydrogen atom, fluorine atom or carbonatoms are 1～4 alkyl.
4. according to the effective gate insulating film of organic crystal described in any one of claim 1～3, the polyimide precursor that comprises the represented structural unit of above-mentioned formula (1) and formula (1a) and this polyimide precursor carry out dehydration closed-loop and the polyimide that obtains, the represented tetracarboxylic dianhydride of following formula (16) and following formula (17) and two represented amine components of (18) to be reacted and the polyimide precursor and the polyimide that obtain
Figure FDA0000459641920000022
In above formula, A, B 1and B 2identical with the definition in above-mentioned formula (1) and formula (1a).
5. an organic transistor, adopts the effective gate insulating film of organic crystal described in any one of claim 1～4 to obtain.
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