CN104684966A - Polyimide, and heat resistant material - Google Patents

Polyimide, and heat resistant material Download PDF

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Publication number
CN104684966A
CN104684966A CN201380050968.9A CN201380050968A CN104684966A CN 104684966 A CN104684966 A CN 104684966A CN 201380050968 A CN201380050968 A CN 201380050968A CN 104684966 A CN104684966 A CN 104684966A
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polyimide
formula
base
heat
carbonatoms
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CN104684966B (en
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长谷川匡俊
石井淳一
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention aims to provide a polyimide exhibiting excellent heat resistance, and a heat resistant material formed from said polyimide. The polyimide has a repeating unit represented by formula (1). (In formula (1), X1 represents a C6-14 quadrivalent aromatic group which may be substituted with a C6-20 aromatic group, for example, X1 represents a quadrivalent group represented by formulae (2) to (4).)

Description

Polyimide and heat-resisting material
Technical field
The present invention relates to polyimide and heat-resisting material.
Background technology
Now, be improved as main purpose with the lightweight of various image display device, solar cell, vulnerability, carry out the research that unorganic glass substrate will be replaced into plastic base.But, for acquisition, there is the equal characteristic of glass, that is, colorless transparency, excellent low thermal expansion characteristics and super thermotolerance, and the desirable plastic substrate material that the vulnerability of the defect as glass is significantly improved, be extremely difficult when current art.
All aromatic polyimide has the highest thermotolerance (solder heat resistance) in existing resin, is therefore applied to the component of the various uses centered by person in electronics.
But consumingly painted (such as non-patent literature 1), in addition, the low thermal expansion characteristics of the height required in order to various Technological adaptability may not be abundant because the Charger transfer deriving from molecular structure interacts for polyimide film in the past.
Therefore, it is difficult for existing polyimide film not being carried out any characteristic improvement and directly applying to the optical components such as plastic base.
On the other hand, disclose following technology: use ester ring type monomer by any one or both of the diamines of the monomer as polyimide or tetracarboxylic dianhydride, thus hinder Charger transfer to interact significantly and by complete for polyimide water white transparency (such as non-patent literature 2 ~ 4).
But, in this case, owing to importing the alicyclic structure unit of poor heat resistance in polyimide backbone, therefore compared with all aromatic polyimide in the past, the significantly reduction of thermostability can not be avoided.In addition, alicyclic structure imports the linear reduction also causing polyimide main chain, and therefore transparent polyimide does not often manifest low thermal expansion characteristics.
Like this, as plastic base, ideally meet and all require that characteristic is not easy on design of material.
On the other hand, according to purposes, sometimes require that the some restrictions in above-mentioned characteristic require the plastic substrate material becomed privileged in characteristic.As an example, the plastic base used in Organic Light Emitting Diode (OLED) indicating meter of top light emitting (top-emission) mode can be enumerated.
In the OLED display purposes of existing bottom-emission mode, plastic base is formed in the process of luminous element, experience more than 300 DEG C, the high-temperature technology of more than 400 DEG C sometimes, if therefore produce volatile organic compounds (VOC) by baseplate material itself in this operation, then likely serious detrimentally affect is brought to element.
Therefore, as OLED plastic substrate material, require to have concurrently high temperature range as far as possible all suppresses VOC to occur extremely high thermostability, thermal dimensional stability highly (namely, low thermal expansion characteristics), the material in the past do not had of the film Forming ability (film toughness) of the equal colorless transparency of glass and excellence, but using all these require that the obstacle that characteristic is developed as the resin material of target is extremely high.
On the other hand, from the profitability of high-precision refinement etc., recently, have studied the OLED display of top light emitting mode.In this approach, the light sent from luminescent layer is being removed with plastic base reverse direction, and therefore send light not by plastic base, the painted of plastic base itself is not significant problem.
Therefore, in the OLED display plastic base of top light emitting mode, require that (can't help baseplate material itself produces the character of VOC for extremely high VOC rejection ability.Identical below.), extremely low coefficient of linear thermal expansion (hereinafter referred to as CTE) and excellent film Forming ability (film toughness).
But, present situation be top light emitting mode OLED display plastic base required by these require that the practicality material that characteristic also all realizes simultaneously is unknown.
In order to VOC rejection ability is increased to the limit, expect from the structure of material resin, get rid of such poor heat resistance such as aliphatic alkyl, thioether group, sulfuryl, amido, carbonate group, urea groups, carbamate groups, amide group, ester group, alkylidene group, isopropylidene, cyclohexylene completely substituting group, connection base.
On the other hand, from the view point of the low thermal expansion characteristics performance of height, expect to become extremely upright and outspoken and the backbone structure of straight line.
Therefore, from the view point of VOC rejection ability and low thermal expansion characteristics, as desirable molecular structure, can enumerate using shown in following formula (X1) to the polyparaphenylene of phenylene as repeating unit.
But polyparaphenylene does not have solvability in organic solvent completely, if will carry out being polymerized and obtaining this polyparaphenylene, then can produce precipitation before molecular weight increases, therefore himself is extremely difficult for this polyreaction.
On the other hand, report the polyimide with repeat unit structure shown in following formula (X2) with the upright and outspoken and backbone structure of straight line, itself is completely insoluble in general organic solvent, but in stage of precursor (polyamic acid) of acid amides series solvent solubility with repeat unit structure shown in following formula (X3), can be shaped to membranaceous by solution casting method, it is at high temperature carried out thermal dehydration cyclization (imidization reaction) process, can easily obtain as polyimide film, and the CTE (such as non-patent literature 6) that the display of this film is extremely low.
The acid amides series solvent solvability of the excellence of polyamic acid depends on the Highly solvated ability (such as non-patent literature 6) of the COOH base of the alternatively base in above-mentioned formula (X3).
But, there is the polymer of repeat unit structure such shown in above-mentioned formula (X2), because macromolecular chain winding each other does not almost have, therefore there is this film often fragilityization and completely lose the such significant problem of film Forming ability (such as non-patent literature 5) significantly.
On the other hand, from the view point of thermotolerance, there is the polyphenyl of the super thermotolerance be equal to polyimide also azoles also can as the candidate of the OLED display plastic substrate material of above-mentioned top light emitting mode.
Such as, there is the polyphenyl of repeat unit structure shown in following formula (X4) also azoles completely not for being applied to molecular structure desirable for such use, namely substituting group, connect base, but there is the upright and outspoken and backbone structure of linearity.
In the same manner as polyimide, polyphenyl also itself is completely insoluble in general organic solvent for azoles, if therefore polyphenyl also azoles precursor is solvable in a solvent, then manufacture polyphenyl also via it azoles film is possible in theory.
But, in order to obtain polyphenyl also azoles precursor, needs operation monomer being converted in advance reactive derivative, with do not need completely such operation polyimide precursor polymerization process compared with, polyphenyl is also the polymerization process of azoles precursor is quite complicated.
Except this point, if show as target with VOC rejection ability and low thermal expansion characteristics, as illustrated in above-mentioned formula (X4), from polyphenyl also get rid of completely in azoles and connect after base, to become upright and outspoken and the mode of the high backbone structure of rectilinearity carries out molecular designing, then produce continuous cropping be polyphenyl also the stage solvability also lacked in organic solvent of the polyhydroxyamide of azoles precursor lacks such significant problem (such as non-patent literature 7).
This is because such as, the solvating ability with the substituting group phenol OH base of the polyhydroxyamide of repeat unit structure shown in following formula (X5) is weak.
According to such situation, directly usual used 2 easy stage film making process during application manufacture polyimide film, that is, carry out the operation of thermal dehydration cyclization, manufacture polyphenyl also after the coating, drying of precursor varnish azoles film is difficult.
As the situation employing polyimide, be suitable for easy manufacturing process (being easy to precursor polymeric operation and ensuing 2 stepwise heating film making process) as long as can obtain, and do not have lack thermotolerance substituting group, connect base but there is the upright and outspoken and new polyphenyl of the backbone structure that rectilinearity is high also azoles, then can be provided in material useful especially as above-mentioned plastic substrate material in above-mentioned technical field, but such material remains the unknown.
Prior art document
Non-patent literature
Non-patent literature 1:Prog.Polym.Sci., 26,259-335 (2001).
Non-patent literature 2:React.Funct.Polym., 30,61-69 (1996).
Non-patent literature 3:Macromolecules, 32,4933-4939 (1999).
Non-patent literature 4:Macromol.Res., 15,114-128 (2007).
Non-patent literature 5:High Perform.Polym., 21,709-728 (2009).
Non-patent literature 6:J.Polym.Sci., Part A, 25,2479-2491 (1987).
Non-patent literature 7:J.Photopolym.Sci.Technol., 17,253-258 (2004).
Summary of the invention
Invent problem to be solved
The present invention proposes in view of the foregoing, its object is to provide and there is low coefficient of linear thermal expansion, high glass-transition temperature, high heat resistance and high film toughness, particularly can contribute to the lightweight of element, the polyimide of vulnerability improvement by being applied to the baseplate material of the such device of such as organic EL.
For solving the method for problem
The present inventor etc. conduct in-depth research to achieve these goals and repeatedly, found that: by comprising benzo the diamine compound of azoles base and aromatic tetracarboxylic acid's dianhydride derive, not there is in molecule the substituting group of poor heat resistance, connect the characteristic required by OLED display plastic substrate material that the polyimide shown in following formula (1) of base demonstrates top light emitting mode especially, namely, extremely high VOC rejection ability, the low thermal expansion characteristics of height and the film Forming ability of excellence, thus complete the present invention.
That is, the invention provides:
1. there is the polyimide of repeating unit shown in formula (1),
(in formula (1), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.)
2. according to 1. polyimide, above-mentioned X 1for being selected from least a kind of 4 valency group in formula (2) ~ formula (4),
3. according to 1. or 2. polyimide, it is characterized in that, be that the polyimide precursor with repeating unit shown in formula (5) of more than 0.3dL/g carries out cyclodehydration and obtains by limiting viscosity,
(in formula (5), X 1represent implication same as described above.)
4. a heat-resisting material, it comprises the polyimide described in any one of 1. ~ 3.,
5. a heat-resistant film, it is made up of the heat-resisting material of 4.,
6. according to 5. heat-resistant film, thickness is 1 ~ 100 μm,
7. according to 5. or 6. heat-resistant film, it is characterized in that having the coefficient of linear thermal expansion of below 15ppm/K, the second-order transition temperature of more than 370 DEG C, 5% weight in nitrogen atmosphere with more than 570 DEG C reduces temperature, and there is the elongation at break of more than 20%
8. a substrate for photo-electric conversion element, luminous element or electronic circuit, it comprises the heat-resistant film described in any one of 5. ~ 7.,
9. a varnish, it comprises the polyimide precursor with repeating unit shown in formula (5),
(in formula (5), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.)
10. according to 9. varnish, above-mentioned X 1for being selected from least a kind of 4 valency group in formula (2) ~ formula (4),
11. according to 9. or 10. varnish, the limiting viscosity of above-mentioned polyimide precursor is more than 0.3dL/g,
The manufacture method of 12. 1 kinds of heat-resistant films, is characterized in that, is coated on substrate, it is heated the varnish described in any one of 9. ~ 11. more than 350 DEG C,
13. polyimide precursors with repeating unit shown in formula (5),
(in formula (5), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.)
14. according to 13. polyimide precursor, its limiting viscosity is more than 0.3dL/g.
The effect of invention
Polyimide of the present invention not only has the low-down coefficient of linear thermal expansion required for dimensional stability of the extremely high thermostability of realization, height, and has very high second-order transition temperature and excellent film toughness concurrently.Therefore, polyimide of the present invention is suitable for baseplate material, particularly the OLED display plastic substrate material of that require these characteristics in recent years, that photo-electric conversion element, luminous element, image display device etc. are such electron device, can contribute to the lightweight of equipment, vulnerability is improved.
Accompanying drawing explanation
The FT-IR spectrum of the polyimide precursor film of Fig. 1 described in embodiment 1.
The FT-IR spectrum of the Kapton of Fig. 2 described in embodiment 1.
Embodiment
Below, the present invention is described in detail.
< polyimide >
Polyimide of the present invention has repeating unit shown in formula (1).
In formula (1), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.
As the concrete example of 4 valency aromatic series bases of such carbonatoms 6 ~ 14, benzene-1 can be enumerated, 2, 4, 5-tetra-base, benzene-1, 2, 3, 4-tetra-base, naphthalene-1, 2, 3, 4-tetra-base, naphthalene-1, 2, 5, 6-tetra-base, naphthalene-1, 2, 6, 7-tetra-base, naphthalene-1, 2, 7, 8-tetra-base, naphthalene-2, 3, 5, 6-tetra-base, naphthalene-2, 3, 6, 7-tetra-base, naphthalene-1, 4, 5, 8-tetra-base, biphenyl-2, 2 ', 3, 3 '-four base, biphenyl-2, 3, 3 ', 4 '-four base, biphenyl-3, 3 ', 4, 4 '-four base, anthracene-1, 2, 3, 4-tetra-base, anthracene-1, 2, 5, 6-tetra-base, anthracene-1, 2, 6, 7-tetra-base, anthracene-1, 2, 7, 8-tetra-base, anthracene-2, 3, 6, 7-tetra-base, luxuriant and rich with fragrance-1, 2, 3, 4-tetra-base, luxuriant and rich with fragrance-1, 2, 5, 6-tetra-base, luxuriant and rich with fragrance-1, 2, 6, 7-tetra-base, luxuriant and rich with fragrance-1, 2, 7, 8-tetra-base, luxuriant and rich with fragrance-1, 2, 9, 10-tetra-base, luxuriant and rich with fragrance-2, 3, 5, 6-tetra-base, luxuriant and rich with fragrance-2, 3, 6, 7-tetra-base, luxuriant and rich with fragrance-2, 3, 9, 10-tetra-base, luxuriant and rich with fragrance-3, 4, 5, 6-tetra-base, luxuriant and rich with fragrance-3, 4, 9, 10-tetra-base, phenyl ether-3, 3 ', 4, 4 '-four base, quinhydrones-diphthalic anhydrides-four base etc.X in repeating unit 1can be the same or different.
Wherein, X 1be preferably benzene-1,2,4,5-tetra-base, naphthalene-1,2,3,4-tetra-base, naphthalene-1,2,5,6-tetra-base, naphthalene-1,2,6,7-tetra-base, naphthalene-1,2,7,8-tetra-base, naphthalene-2,3,5,6-tetra-base, biphenyl-2,2 ', 3,3 '-four base, biphenyl-2,3,3 ', 4 '-four base, biphenyl-3,3 ', 4,4 '-four base, is more preferably any one of following formula (2) ~ formula (4).
In polyimide of the present invention, any hydrogen atom on the aromatic nucleus of 4 valency aromatic series bases of the carbonatoms 6 ~ 14 in repeating structure can be replaced by the aromatic series base of carbonatoms 6 ~ 20.
As the concrete example of the aromatic series base of such carbonatoms 6 ~ 20, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl etc. can be enumerated.
< polyimide precursor >
Polyimide of the present invention can be manufactured by the polyimide precursor with repeating unit shown in following formula (5).
(in formula (5), X 1represent implication same as described above.)
The method that manufacture has the polyimide precursor of repeating unit shown in above-mentioned formula (5) is not particularly limited, and can apply known method.More specifically, such as, obtain by the following method.
First, diamines (corresponding with the diamines shown in the formula (6) obtained by aftermentioned method) shown in following formula (8) is dissolved in solvent, slowly add the tetracarboxylic dianhydride shown in following formula (7) wherein, use mechanical stirrer, stir 0.5 ~ 100 hour, preferably 1 ~ 72 hour 0 ~ 100 DEG C, preferably 20 ~ 60 DEG C.
(in formula (7), X 1represent implication same as described above.)
Now, amount (mol) ratio of the acid dianhydride shown in the diamines shown in formula (8) and formula (7) is relative to diamines 1, can be acid dianhydride about 0.8 ~ 1.1, be preferably about 0.9 ~ 1.1, be more preferably about 0.95 ~ 1.05.
In addition, the concentration of the monomer (diamines and acid dianhydride) in reaction solvent is 5 ~ 50 quality %, is preferably 10 ~ 40 quality %.By being polymerized in this monomer concentration scope, thus can fully guarantee monomer and structure adaptability, can obtain evenly and the solution of the polyimide precursor of high-polymerization degree.
From the view point of the toughness of heat-resistant film of the present invention, expect that the polymerization degree of polyimide precursor is as far as possible high, therefore, expect to make the monomer concentration in reaction solvent be 5 ~ 50 quality %, be preferably 10 ~ 40 quality % to modulate polyimide precursor.
In addition, excessively increase in the polymerization degree of polyimide precursor, when polymeric solution becomes and not easily stirs, also can with react the solvent phase that uses with solvent suitably dilute.
In addition, from the view point of the operation of the varnish that toughness and the manufacture thereof of heat-resistant film of the present invention use, the limiting viscosity of polyimide precursor is preferably more than 0.3dL/g, is more preferably in the scope of 0.3 ~ 5.0dL/g.
Such as the thermostability that the polyimide performance of object is extremely high from the view point of making in the present invention, when being polymerized polyimide, the aromatic tetracarboxylic acid's dianhydride not containing the substituting group beyond phenyl, the connection base beyond ether completely can be used.Even if the use of ester ring type tetracarboxylic acid is a small amount of, also likely damage thermostability significantly, therefore not preferred.
As such aromatic tetracarboxylic acid's dianhydride, as long as meet above-mentioned condition, be just not particularly limited, can pyromellitic acid anhydride be enumerated, benzene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, naphthalene-1,2,7,8-tetracarboxylic acid dianhydride, naphthalene-2,3,5,6-tetracarboxylic acid dianhydride, naphthalene-2,3,6,7-tetracarboxylic acid dianhydride, naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid dianhydride, biphenyl-2,2 ', 3,3 '-tetracarboxylic acid dianhydride, biphenyl-2,3,3 ', 4 '-tetracarboxylic acid dianhydride, biphenyl-3,3 ', 4,4 '-tetracarboxylic acid dianhydride, anthracene-1,2,3,4-tetracarboxylic acid dianhydride, anthracene-1,2,5,6-tetracarboxylic acid dianhydride, anthracene-1,2,6,7-tetracarboxylic acid dianhydride, anthracene-1,2,7,8-tetracarboxylic acid dianhydride, anthracene-2,3,6,7-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,3,4-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-1,2,5,6-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-1,2,6,7-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-1,2,7,8-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-1,2,9,10-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-2,3,5,6-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-2,3,6,7-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-2,3,9,10-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-3,4,5,6-tetracarboxylic acid dianhydrides, luxuriant and rich with fragrance-3,4,9,10-tetracarboxylic acid dianhydrides, 4,4 '-oxygen base two O-phthalic acid dianhydride, quinhydrones-diphthalic anhydrides etc. as an example.They may be used alone, two or more kinds can also be used in combination.
In above-mentioned aromatic tetracarboxylic acid's dianhydride, in order to obtain polyimide of the present invention, the viewpoint such from the view point of exhibiting low thermal expansion characteristics and obtain easiness, cost, preferably uses and has tetracarboxylic dianhydride that the is upright and outspoken and structure of straight line, namely, pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride is as tetracarboxylic dianhydride's composition.Now, the content of these tetracarboxylic dianhydrides is 50 ~ 100 % by mole of whole tetracarboxylic dianhydride's usage quantity, is preferably 70 ~ 100 % by mole.
The thermostability extremely high from the view point of polyimide of the present invention performance is such, as comprising benzo illustrated in above-mentioned formula (8) the copolymer composition of the diamines of azoles base, partly can use the aromatic diamine not containing the substituting group beyond phenyl, the connection base beyond ether completely.Wherein, even if the use of ester ring type diamines is a small amount of, also likely damage thermostability significantly, therefore not preferred.
As such aromatic diamine, as long as in the scope of above-mentioned condition, just be not particularly limited, Ursol D can be enumerated, mphenylenediamine, O-Phenylene Diamine, 4, 4 '-diamino-diphenyl ether, 3, 4 '-diamino-diphenyl ether, 3, 3 '-diamino-diphenyl ether, 2, 4 '-diamino-diphenyl ether, 2, 2 '-diamino-diphenyl ether, p-diaminodiphenyl, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 4, 4 '-bis-(4-amino-benzene oxygen) biphenyl, p-terphenyl diamines etc. as an example.In addition, they may be used alone, two or more kinds can also be used.The usage quantity of these copolymerized diamine compositions is 0 ~ 30 % by mole of whole diamines usage quantity, is preferably 0 ~ 10 % by mole.
As the solvent used during polymerization polyimide precursor of the present invention, preferred use N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, methyl-sulphoxide, 3-methoxyl group-N, N-dimethylpropane acid amides, 3-n-butoxy-N, N-dimethylpropane acid amides, 3-sec-butoxy-N, N-dimethylpropane acid amides, 3-tert.-butoxy-N, the non-protonic solvents such as N-dimethylpropane acid amides, as long as the polyimide precursor of starting monomer and generation dissolves, just no problem, its structure is not particularly limited.
Can use such as, N, dinethylformamide, N, phenol series solvent, methyl phenyl ketone, DMI, tetramethylene sulfone, the methyl-sulphoxides etc. such as the glycol such as carbonate solvent, triglycol series solvent, meta-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol such as cyclic ester solvent, ethylene carbonate, the Texacar PCs such as the amide solvents such as N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, gamma-butyrolactone, γ-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolactone.
In addition, the general solvent such as phenol, ortho-cresol, butylacetate, ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether, tetrahydrofuran (THF), diethylene glycol dimethyl ether, methyl iso-butyl ketone (MIBK), diisobutyl ketone, pimelinketone, methyl ethyl ketone, acetone, butanols, ethanol, dimethylbenzene, toluene, chlorobenzene also can partly use.
The polymeric solution of polyimide precursor of the present invention directly can be used in order to manufacture heat-resistant film of the present invention, in order to manufacture heat-resistant film of the present invention also can be used in the poor solvents such as a large amount of water, methyl alcohol carry out dripping, filter, dry and obtain polyimide precursor, it is dissolved in again solvent (solvent etc. used in the manufacture of above-mentioned polyimide precursor) and the material that obtains.In addition, the polymeric solution of above-mentioned polyimide precursor and the material making polyimide precursor again be dissolved in solvent and obtain are all the varnish comprising polyimide precursor, are objects of the present invention.
< heat-resistant film (polyimide film) >
Heat-resistant film of the present invention can manufacture by the polyimide precursor obtained by aforesaid method being carried out thermal dehydration cyclization (imidization reaction).
That is, heat-resistant film of the present invention manufactures as follows.
To varnish curtain coating on the substrates such as glass, copper, aluminium, stainless steel, silicon of polyimide precursor of the present invention be comprised, and carry out drying 40 ~ 180 DEG C, preferably 50 ~ 150 DEG C in an oven, make polyimide precursor film.
By by the polyimide precursor film of gained on substrate in a vacuum, in the non-active gas such as nitrogen or carry out heating in air and obtain heat-resistant film of the present invention (polyimide film).
Now, such from the view point of end imidization reaction, Heating temperature is more than 200 DEG C, is preferably more than 250 DEG C, and from the view point of suppressing, the thermolysis of the polyimide film generated is such, and Heating temperature is less than 450 DEG C, is preferably less than 430 DEG C.
In addition, expect that imidization carries out in a vacuum or in non-active gas, as long as imidization temperature is not too high, then can carry out in atmosphere.
In imidization reaction, also can replace thermal treatment and pass through polyimide precursor film under the existence of the tertiary amine such as pyridine, triethylamine, impregnated in the solution containing cyclodehydration reagent such as diacetyl oxides and carry out.
In addition, also these cyclodehydration reagent at room temperature can be put in the varnish comprising polyimide precursor in advance and stir, it is carried out curtain coating, drying on aforesaid substrate, thus make the polyimide precursor film of partly imidization, by it being heat-treated as described above further, polyimide film can be obtained.
After the varnish comprising polyimide precursor of the present invention being coated on tinsel, such as Copper Foil carry out drying, utilize above-mentioned condition to carry out imidization, thus the multilayer body of metal level and polyimide film can be obtained.Then use the etching solutions such as ferric chloride in aqueous solution by the circuit shape desired by etching metal layer one-tenth, thus adhesive-free type flexible printed board can be manufactured.
The thickness of heat-resistant film of the present invention is not particularly limited, as long as suitably determine thickness according to application target, if when being used as the substrate of the such luminous element of the such photo-electric conversion element of organic solar batteries, silicon solar cell, organic EL, electric circuit electronics technical by this heat-resistant film itself, about 1 ~ 100 μm is applicable.
Heat-resistant film of the present invention described above easily can be manufactured by the precursor with the polyimide of excellent film Forming ability of the present invention, there is the low thermal expansion characteristics of extremely high VOC rejection ability and height, therefore can be suitable as the film of the thermotolerance in the substrate of organic EL, liquid crystal display device, organic solar batteries etc.
< comprises benzo the synthesis > of the diamines (diamines hereinafter also referred to as containing BO) of azoles base
Polyimide precursor of the present invention and polyimide as described above, are obtained by the tetracarboxylic dianhydride as monomer whose and the diamines containing BO.
Diamines containing BO base used in the present invention represents with following formula (8).
The diamines containing BO base shown in above-mentioned formula (8) uses two (Ortho-Aminophenol) shown in following formula (9) to synthesize as starting raw material.
Below, about employing 3,3 '-dihydroxybiphenyl amine is (hereinafter referred to as p-HAB.) as the synthetic method containing the diamines of BO base when two (Ortho-Aminophenol), an example of step is illustrated, but synthetic method is not particularly limited, known method can be applied.
First, in 3 mouthfuls of flasks, p-HAB is dissolved in the acid amides series solvent dewatered well, adds pyridine wherein as de-acidying agent, carry out sealing with dottle pin lid and make A liquid.
Next, in eggplant type flask, the 4-nitrobenzoyl chloride of 2 of p-HAB times of molar weights is dissolved in the solvent same with A liquid, carries out sealing with dottle pin lid and make B liquid.
And then, A liquid is cooled in ice bath, utilizes rotor to carry out stirring and utilize syringe to be added in A liquid by each for B liquid a small amount of gradation, add and terminate rear continuation stirred for several hour, synthesize diamide body.
Next, remove ice bath, at room temperature after stirred for several hour, react to make cyclodehydration and terminate and in this reaction soln, add the tosic acid of appropriate amount, utilize the oil bath of 200 DEG C to carry out a few hours backflow.
By the throw out that collecting by filtration generates, after water repetitive scrubbing, 100 DEG C of vacuum-dryings 12 hours, synthesize the dinitro matrix shown in following formula (10),
Next, in 3 mouthfuls of flasks, the dinitro matrix shown in above-mentioned formula (10) is dissolved in acid amides series solvent, adds the Pd/C of appropriate amount as catalyzer, in hydrogen atmosphere, DEG C carry out 1 ~ 24 hour reduction reaction in room temperature ~ 150.The carrying out of reaction can be followed the trail of by thin-layer chromatography.
After reaction terminates, after filtering to isolate Pd/C, filtrate is dropped in large water gaging at leisure resultant is separated out.By collected by filtration thing, after water repetitive scrubbing, 100 DEG C of vacuum-dryings 12 hours.Also can carry out recrystallize from suitable solvent as required and carry out high purity.
Like this, the diamines containing BO base shown in following formula (6) of the polymerization that may be used for polyimide precursor of the present invention can be obtained.
Embodiment
Below, specifically describe the present invention by embodiment, but the present invention is not limited to these embodiments.In addition, the physics value in following example measures by the following method.
< infrared absorption spectrum >
Use fourier-transform infrared spectrophotometer (Japanese light splitting society FT-IR5300), utilize KBr plate method to measure the infrared absorption spectrum of the diamines containing BO base.In addition penetrant method is utilized to measure the infrared absorption spectrum of polyimide precursor film and polyimide film (about 5 μm thick).
< 1h-NMR spectrum >
Use NEC society NMR spectrophotometer (ECP400), in deuterated dimethylsulfoxide, measure the diamines containing BO base 1h-NMR spectrum.
< differential scanning calorimetric analysis (fusing point and melting curve) >
Use Block ル カ ー エ イ エ ッ Network ス society's differential scanning calorimetric analysis device (DSC3100), in nitrogen atmosphere, measure fusing point and the melting curve of the diamines containing BO base with heat-up rate 2 DEG C/min.Fusing point is higher, and melting peak is more sharp-pointed, represents that purity is higher.
< limiting viscosity >
Ostwald's viscometer is used to measure 30 DEG C of polyimide precursor solution to 0.5 quality %.
< second-order transition temperature (T g) >
Block Le カ ー エ イ エ ッ Network ス society is used to heat mechanical analytical equipment (TMA4000), by Measurement of Dynamic Viscoelasticity, obtained the second-order transition temperature of polyimide film (20 μm thick) by the peak temperature of expended energy curve when frequency 0.1Hz, heat-up rate 5 DEG C/min.
< coefficient of linear thermal expansion: CTE >
Block Le カ ー エ イ エ ッ Network ス society is used to heat mechanical analytical equipment (TMA4000), pass through thermo-mechanical analysis, by the elongation of test film when loading 0.5g/ thickness 1 μm, heat-up rate 5 DEG C/min, the mean value as the scope of 100 ~ 200 DEG C obtains the CTE of polyimide film (20 μm thick).
< 5% weight reduces temperature (T d 5) >
Block ル カ ー エ イ エ ッ Network ス society is used to heat gravimetric analysis device (TG-DTA2000), with in the temperature-rise period of heat-up rate 10 DEG C/min in nitrogen or in air, the temperature when initial weight measuring polyimide film (20 μm are thick) decreases 5%.These values are higher, represent that thermostability is higher.
< Young's modulus, elongation at break, breaking tenacity >
Use Japan ボ ー Le ドウィン society's tensile testing machine (テ Application シ ロ Application UTM-2), tension test (draw speed: 8mm/ minute) is implemented to polyimide test film (3mm × 30mm × 20 μm thick), obtain Young's modulus by the Initial Gradient of Ying Li – strain curve, elongation when being ruptured by film obtains elongation at break (%).Elongation at break is higher, means that the toughness of film is higher.
[synthesis example 1]
< contains the synthesis > of the diamines of BO base
In 3 mouthfuls of flasks, p-HAB (Wakayama refine society's system, 2.61g, 12mmol) is dissolved in the METHYLPYRROLIDONE that dewatered well (hereinafter referred to as NMP.) in (81mL), add pyridine (2.9mL, 36mmol) wherein as de-acidying agent, carry out sealing with dottle pin lid and make A liquid.Next, in another eggplant type flask, 4-nitrobenzoyl chloride (4.49g, 24mmol) is dissolved in NMP (17mL), carries out sealing with dottle pin lid and make B liquid.A liquid is cooled in ice bath, utilizes rotor to carry out stirring and utilize syringe to be added in A liquid by each for B liquid a small amount of gradation, add and terminate rear continuation stirring 3 hours, synthesize diamide body.
Following removal ice bath, at room temperature after stirred for several hour, reacts to make cyclodehydration and terminates and in this reaction soln, add the tosic acid (1.90g, 11mmol) of appropriate amount, utilize the oil bath of 200 DEG C to carry out 3 hours reflux.By the throw out that filtered and recycled generates, wash with water.Now, repetitive scrubbing does not observe white precipitate until suitably add 1% silver nitrate aqueous solution in washing lotion yet, completely removes chlorion.Then after washing with ethanol, 100 DEG C of vacuum-dryings 12 hours, the yellow needles obtaining fusing point 401 DEG C with yield 81% is brilliant.
The resultant of gained is at DMSO-d 6, CDCl 3in almost insoluble, therefore do not implement 1h-NMR measures, but in its infrared absorption spectrum, at 1605cm -1display BO base C=N stretching vibration band, at 1518/1348cm -1display nitro stretching vibration band, does not observe acid amides C=O stretching vibration band, phenol O-H stretching vibration band.
According to these results, can think that the resultant of gained is for the dinitro matrix shown in following formula (10).
Next, in 3 mouthfuls of flasks, by the dinitro matrix (6.13g shown in above-mentioned formula (10), 11.9mmol) be dissolved in NMP (250mL), add Pd/C (0.63g) as catalyzer, in hydrogen atmosphere, carry out 15 hours reduction reactions at 100 DEG C.The carrying out of reaction is followed the trail of by thin-layer chromatography.After reaction terminates, after filtering to isolate Pd/C, filtrate is dropped in a large amount of water at leisure resultant is separated out.By filtered and recycled throw out, after water repetitive scrubbing, 100 DEG C of vacuum-dryings 12 hours, obtain brown powder with thick resultant yield 82%.In addition, in order to improve purity, carry out recrystallize from gamma-butyrolactone, the brown tabular finally obtaining fusing point 354 DEG C 100 DEG C of vacuum-dryings 12 hours is brilliant.
In the infrared absorption spectrum of the resultant of gained, at 3454/3380/3210cm -1display amino N-H stretching vibration band, at 1621/1607cm -1display BO base C=N stretching vibration band, at 1499cm -1display Isosorbide-5-Nitrae-phenylene stretching vibration band, does not observe nitro stretching vibration band, acid amides C=O stretching vibration band.
By the result of this infrared absorption spectrum and following 1the results verification of H-NMR spectrum and ultimate analysis, the resultant of gained is the diamines containing BO base shown in following formula (6).
1h-NMR spectrum (400MHz, DMSO-d 6, δ, ppm): 8.06 (s, 2H), 7.90-7.88 (d, 4H), 7.75-7.71 (m, 4H), 6.72-6.70 (d, 4H), 6.04 (s, 4H)
Ultimate analysis: presumed value C; 74.63%, H; 4.34%, N; 13.39%, analytical value C; 74.41%, H; 4.47%, N; 13.26%
The evaluating characteristics > of the polymerization of < polyimide precursor, imidization and polyimide film
[embodiment 1]
The diamines 5mmol containing BO base shown in above-mentioned formula (6) is added in the closed reaction vessel of dry well band stirrer, after dissolving at about 50 DEG C in the NMP dewatered fully with molecular sieve 4A, let cool to room temperature, 2 are added in this solution, 3,6,7 '-naphthalenetetracarbacidic acidic dianhydride (JFE ケ ミ カ Le society system, hereinafter referred to as NTDA) powder 5mmol (total soluble matters concentration: 13 quality %).Then, stirring at room temperature 72 hours, obtain evenly and the solution (polyimide precursor solution) comprising polyimide precursor of thickness.
In NMP, ostwald's viscometer is utilized to measure the limiting viscosity of the polyimide precursor obtained for 1.15dL/g at 30 DEG C with the concentration of 0.5 quality %.
Above-mentioned polyimide precursor solution is coated glass substrate, 80 DEG C of dryings 3 hours in hot air dryer, produces polyimide precursor film.
Fig. 1 shows the infrared absorption spectrum of the film of the polyimide precursor of acquisition.At 2600cm -1near observe wide absorption band (hydrogen bond COOH base O-H stretching vibration band), at 1711cm -1observe hydrogen bond COOH base C=O stretching vibration band, at 1678cm -1(shoulder)/1530cm -1observe amide group C=O stretching vibration band, at 1501cm -1observe Isosorbide-5-Nitrae-phenylene stretching vibration band, on the other hand, have no and derive from the amino N-H stretching vibration band of monomer, the anhydride group C=O stretching vibration band of tetracarboxylic dianhydride, therefore confirm the polyimide precursor generating target.
Then, polyimide precursor film is heated 1 hour at 250 DEG C together with glass substrate, within 1 hour, hot-imide is carried out in a vacuum further 350 DEG C of heating, then peel from substrate to remove residual stress, carry out thermal treatment in 1 hour at 400 DEG C in a vacuum further, obtain the polyimide film of the softness of thickness 20 μm.
The infrared absorption spectrum of the polyimide film that Fig. 2 makes under being presented at identical conditions separately.At 3046cm -1observe aromatic series C-H stretching vibration band, at 1777/1721cm -1observe imide C=O stretching vibration band, at 1618cm -1observe BO base C=N stretching vibration band, at 1501cm -1observe Isosorbide-5-Nitrae-phenylene stretching vibration band, at 1356cm -1observe imide N-C (aromatic series) stretching vibration band, on the other hand, have no the absorption band deriving from COOH base, amide group, therefore confirm imidization reaction and finish, generate the polyimide of target.
The polyimide film of gained does not all show solvability completely for any organic solvent.Carry out that Measurement of Dynamic Viscoelasticity obtains as a result, observe glass transition point at 408 DEG C to polyimide film (thickness 20 μm).The extremely low value that coefficient of linear thermal expansion display 8.4ppm/K is such.Can this is presumably because that the backbone structure of polyimide of the present invention is extremely upright and outspoken and rectilinearity is high, therefore in hot-imide operation polyimide main chain in the direction parallel with face orientation significantly.5% weight reduces temperature in nitrogen, is 603 DEG C, and be 592 DEG C in atmosphere, the polyimide of known gained has extremely high thermostability.That further evaluation mechanical characteristics obtains as a result, modulus in tension (Young's modulus) is 3.8GPa, elongation at break is 39%, also maintains excellent film toughness.Physics value is concluded in table 1.
[embodiment 2]
As tetracarboxylic dianhydride's composition, replace NTDA and use 3 of same molar weight, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (with Guang Chun medicine society system, hereinafter referred to as BPDA), in addition, be polymerized polyimide precursor according to the method described in embodiment 1, be filmed, hot-imide, film evaluation of physical property.Physical property shown in table 1.Excellent characteristic is shown in the same manner as the polyimide described in embodiment 1.
In addition, in table, ND represents glass transition do not detected in the Measurement of Dynamic Viscoelasticity of room temperature ~ 500 DEG C.
[embodiment 3]
As tetracarboxylic dianhydride's composition, replace NTDA and use pyromellitic acid anhydride (the Mitsubishi gas chemistry society system of same molar weight, hereinafter referred to as PMDA), in addition, be polymerized polyimide precursor according to the method described in embodiment 1, be filmed, hot-imide, film evaluation of physical property.Physical property shown in table 1.Excellent characteristic is shown in the same manner as the polyimide described in embodiment 1.
[comparative example 1]
Use with the PMDA of molar weight as tetracarboxylic dianhydride's composition, use the Ursol D with molar weight as diamine component, carry out being polymerized according to the method described in embodiment 1, masking, hot-imide, produce polyimide film.The CTE (2.8ppm/K) that the display of this polyimide film is extremely low, but fragile in the extreme, and elongation at break is 0%.In addition, this film easily ruptures due to bending.This is because come from the bar-shaped backbone structure of this polyimide system, the winding between polymer chain does not almost have.
[comparative example 2]
Use with the PMDA of molar weight as tetracarboxylic dianhydride's composition, use with 4 of molar weight as diamine component, 4 '-oxygen base pentanoic, carry out being polymerized according to the method described in embodiment 1, masking, hot-imide, film evaluation of physical property.The second-order transition temperature (408 DEG C) that the display of this polyimide film is extremely high, have the excellent toughness of elongation at break 85%, but CTE is 42.8ppm/K, does not show low thermal expansion characteristics.
[table 1]

Claims (14)

1. there is the polyimide of repeating unit shown in formula (1),
In formula (1), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.
2. polyimide according to claim 1, described X 1for being selected from least a kind of 4 valency group in formula (2) ~ formula (4),
3. polyimide according to claim 1 and 2, is characterized in that, is be that the polyimide precursor with repeating unit shown in formula (5) of more than 0.3dL/g carries out cyclodehydration and obtains by limiting viscosity,
In formula (5), X 1represent implication same as described above.
4. a heat-resisting material, it comprises the polyimide described in any one of claims 1 to 3.
5. a heat-resistant film, it is made up of heat-resisting material according to claim 4.
6. heat-resistant film according to claim 5, thickness is 1 ~ 100 μm.
7. the heat-resistant film according to claim 5 or 6, it is characterized in that, have the coefficient of linear thermal expansion of below 15ppm/K, the second-order transition temperature of more than 370 DEG C, 5% weight in nitrogen atmosphere with more than 570 DEG C reduces temperature, and has the elongation at break of more than 20%.
8. a substrate for photo-electric conversion element, luminous element or electronic circuit, it comprises the heat-resistant film described in any one of claim 5 ~ 7.
9. a varnish, it comprises the polyimide precursor with repeating unit shown in formula (5),
In formula (5), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.
10. varnish according to claim 9, described X 1for being selected from least a kind of 4 valency group in formula (2) ~ formula (4),
11. varnish according to claim 9 or 10, described polyimide precursor has the limiting viscosity of more than 0.3dL/g.
The manufacture method of 12. 1 kinds of heat-resistant films, is characterized in that, is coated on substrate, it is heated the varnish described in any one of claim 9 ~ 11 more than 350 DEG C.
13. polyimide precursors with repeating unit shown in formula (5),
In formula (5), X 14 valency aromatic series bases of the carbonatoms 6 ~ 14 that expression can be replaced by the aromatic series base of carbonatoms 6 ~ 20.
14. polyimide precursors according to claim 13, its limiting viscosity is more than 0.3dL/g.
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