CN104684966B - Polyimides and heat-resisting material - Google Patents

Polyimides and heat-resisting material Download PDF

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CN104684966B
CN104684966B CN201380050968.9A CN201380050968A CN104684966B CN 104684966 B CN104684966 B CN 104684966B CN 201380050968 A CN201380050968 A CN 201380050968A CN 104684966 B CN104684966 B CN 104684966B
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film
heat
polyimides
bases
formula
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CN104684966A (en
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长谷川匡俊
石井淳
石井淳一
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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 problem of the present invention is to provide the polyimides of excellent heat resistance and the heat-resisting material comprising the polyimides.Method as the problem for solving the present invention is the polyimides with repeat unit shown in formula (1).(in formula (1), X1Representing can be by 4 valency aromatic series base of the carbon number 6~14 that the aromatic series base of carbon number 6~20 substitutes, for example, such 4 valency groups shown in formula (2)~formula (4)).

Description

Polyimides and heat-resisting material
Technical field
The present invention relates to polyimides and heat-resisting material.
Background technology
Now, main purpose is improved as with various image display devices, the lightweight of solar cell, fragility, carried out Unorganic glass substrate is replaced into the research of plastic base.However, for obtaining with the equal characteristic of glass, i.e. nothing Transparent, the excellent low thermal expansion characteristics of color and super heat resistance, and significantly improved as fragility the defects of glass Preferable plastic substrate material, be extremely difficult in the case of current art.
All aromatic polyimides has highest heat resistance (solder heat resistance) in existing resin, therefore is applied to The component of various uses centered on person in electronics.
However, conventional polyimide film is consumingly coloured due to the electric charge transfer interaction from molecular structure (such as non-patent literature 1), in addition, the low thermal expansion characteristics of the height required for various Technological adaptabilities may not be abundant.
Therefore, existing polyimide film is improved without any characteristic and directly applies to the optics structure such as plastic base Part is difficult.
On the other hand, following technologies are disclosed：Pass through the diamines for the monomer for being used as polyimides or appointing for tetracarboxylic dianhydride One or both uses ester ring type monomer, so as to significantly hinder electric charge transfer to interact that polyimides is completely colorless Brightization (such as non-patent literature 2~4).
However, in this case, due to the alicyclic structure unit of the importing poor heat resistance in polyimide backbone, therefore with Conventional all aromatic polyimides is compared, it is impossible to avoids being greatly reduced for heat endurance.Also cause in addition, alicyclic structure imports The linear reduction of polyimides main chain, therefore transparent polyimide does not often show low thermal expansion characteristics.
So, as plastic base, ideally meet all to require that characteristic is not easy on design of material.
On the other hand, according to purposes, sometimes require that what some restrictions in above-mentioned characteristic were becomed privileged in terms of requiring characteristic Plastic substrate material.As one, the Organic Light Emitting Diode (OLED) of top light emitting (top-emission) mode can be enumerated Plastic base used in display.
In the OLED display purposes of existing bottom-emission mode, the process of light-emitting component is formed on plastic base In, the high-temperature technology of more than 300 DEG C, sometimes more than 400 DEG C of experience, so if being produced in itself by baseplate material in the process VOC (VOC), it is likely that serious harmful effect is brought to element.
Therefore, as OLED plastic substrate materials, it is desirable to have the pole that high temperature range as far as possible all suppresses VOC generations concurrently The equal colorless transparency of its high heat endurance, thermal dimensional stability (that is, low thermal expansion characteristics), the glass of height and excellent Film Forming ability (film toughness) in the past without material, but whole these requirements characteristics are opened as the resin material of target The obstacle of hair is extremely high.
On the other hand, from the profitability of High precision etc., recently, the OLED that have studied top light emitting mode is shown Device.In this approach, it is removed from the light that luminescent layer is sent with plastic base opposite direction, therefore sends light and do not pass through plastics Substrate, the coloring of plastic base in itself are not significant problems.
Therefore, in the OLED display plastic base of top light emitting mode, it is desirable to extremely high VOC rejection abilities (do not produce VOC property in itself by baseplate material.It is same as below.), extremely low coefficient of linear thermal expansion (hereinafter referred to as CTE) and Excellent film Forming ability (film toughness).
However, present situation is the these requirements characteristic required by the OLED display plastic base of top light emitting mode The practicality material all realized simultaneously is unknown.
In order to which VOC rejection abilities are improved to the limit, it is expected from the structure of material resin to exclude completely aliphatic alkyl, Thioether group, sulfuryl, amido, carbonate group, urea groups, carbamate groups, amide groups, ester group, alkylidene, isopropylidene, ring are sub- The substituent of poor heat resistance, linker as hexyl etc..
On the other hand, from the viewpoint of the low thermal expansion characteristics performance of height, it is expected to turn into extremely upright and outspoken and straight line Backbone structure.
Therefore, from the viewpoint of VOC rejection abilities and low thermal expansion characteristics, as preferable molecular structure, can enumerate Using the polyparaphenylene to phenylene as repeat unit shown in following formula (X1).
However, polyparaphenylene does not have dissolubility completely in organic solvent, this poly- pair is obtained if to be polymerize Phenylene, then can produce precipitation before molecular weight increase, therefore its own is extremely difficult for the polymerisation.
On the other hand, report with upright and outspoken and straight line backbone structure with repeat unit knot shown in following formula (X2) The polyimides of structure, itself is fairly insoluble in general organic solvent, but with repeat unit shown in following formula (X3) In the stage of the soluble precursor (polyamic acid) of the acid amides series solvent of structure, membranaceous, general can be shaped to by solution casting method It carries out thermal dehydration cyclization (imidization reaction) processing at high temperature, easily can be obtained as polyimide film , and the film shows extremely low CTE (such as non-patent literature 6).
The COOH as substituent that the excellent acid amides series solvent dissolubility of polyamic acid is depended in above-mentioned formula (X3) The Highly solvated ability (such as non-patent literature 6) of base.
However, the macromolecule with such repeat unit structure shown in above-mentioned formula (X2), because macromolecular chain is mutual Winding almost do not have, therefore with the film usually significantly fragilityization and completely lose significant problem as film Forming ability (such as non-patent literature 5).
On the other hand, from the viewpoint of heat resistance, there is the polyphenyl for the super heat resistance being equal to polyimides simultaneouslyAzoles Can also be as the candidate of the OLED display plastic substrate material of above-mentioned top light emitting mode.
For example, the polyphenyl with repeat unit structure shown in following formula (X4) is simultaneouslyAzoles is not completely for applied to upper Preferable molecular structure, i.e. substituent, linker for purposes are stated, but there is upright and outspoken and linear backbone structure.
In the same manner as polyimides, polyphenyl is simultaneouslyItself is fairly insoluble in general organic solvent for azoles, so if Polyphenyl is simultaneouslyAzoles precursor is solvable in a solvent, then manufactures polyphenyl simultaneously via itAzoles film is possible in theory.
However, in order to obtain polyphenyl simultaneouslyAzoles precursor, it is necessary to by monomer pre-conversion be reactive derivative process, with Compared completely without the polymerization process of the polyimide precursor of such process, polyphenyl is simultaneouslyThe polymerization process phase of azoles precursor Work as complexity.
In addition to this point, if showing as target with VOC rejection abilities and low thermal expansion characteristics, such as above-mentioned formula (X4) It is illustrated such, from polyphenyl simultaneouslyAfter excluding linker completely in azoles, with as upright and outspoken and high linearity backbone structure Mode carries out MOLECULE DESIGN, then produce continuous cropping be polyphenyl simultaneouslyThe stage of the polyhydroxyamide of azoles precursor also lacks organic molten Significant problem (such as non-patent literature 7) as dissolubility shortage in agent.
Because for example, substituent phenol with the polyhydroxyamide of repeat unit structure shown in following formula (X5) The solvability of OH bases is weak.
Commonly used easy 2 stages film work during according to such situation, directly application manufacture polyimide film Sequence, i.e. in being coated with of precursor varnish, dry after carry out the process of thermal dehydration cyclization, to manufacture polyphenyl simultaneouslyAzoles film is Difficult.
As the situation for having used polyimides, as long as the manufacturing process for being suitable for simplicity can be obtained (before readily Body polymerization process and ensuing 2 stepwise heating film making process), and without substituent, linker but the tool for lacking heat resistance There is the new polyphenyl of upright and outspoken and high linearity backbone structure simultaneouslyAzoles, then it can be provided in above-mentioned technical field as upper The particularly advantageous material of plastic substrate material is stated, but such material is still unknown.
Prior art literature
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).
The content of the invention
Invent problem to be solved
The present invention is to propose in view of the foregoing, and its object is to provide with low coefficient of linear thermal expansion, high glass Change transition temperature, high-fire resistance and high film toughness, particularly can be by applied to device as such as organic EL element Baseplate material and contribute to the lightweight of element, fragility improve polyimides.
For solving the method for problem
Further investigation has been repeated in the present inventor etc. to achieve these goals, as a result finds：By including benzo The diamine compound of oxazolyl derives with aromatic tetracarboxylic acid's dianhydride, substituent of the intramolecular without poor heat resistance, linker Polyimides shown in following formula (1) is where it is particularly shown that required by the OLED display plastic substrate material of top light emitting mode Characteristic, i.e. extremely high VOC rejection abilities, the low thermal expansion characteristics of height and excellent film Forming ability, so as to complete this Invention.
That is, the present invention provides：
1. the polyimides with repeat unit shown in formula (1),
(in formula (1), X1Expression can be by 4 valencys of the carbon number 6~14 that the aromatic series base of carbon number 6~20 substitutes Aromatic series base.)
2. according to 1. polyimides, above-mentioned X1For at least one kind of 4 valency group in formula (2)~formula (4),
3. according to 1. or 2. polyimides, it is characterised in that be that inherent viscosity is had into formula for more than 0.3dL/g (5) polyimide precursor of repeat unit shown in is carried out obtained by cyclodehydration,
(in formula (5), X1Represent implication same as described above.)
4. a kind of heat-resisting material, it includes the polyimides described in 1.~3. any one,
5. a kind of heat-resistant film, it is made up of 4. heat-resisting material,
6. according to 5. heat-resistant film, thickness is 1~100 μm,
7. according to 5. or 6. heat-resistant film, it is characterised in that the coefficient of linear thermal expansion with below 15ppm/K, 370 Glass transition temperature more than DEG C, temperature is reduced with more than 570 DEG C of 5% weight in nitrogen atmosphere, and with 20% Elongation at break above,
8. the substrate of a kind of photo-electric conversion element, light-emitting component or electronic circuit, it includes 5.~7. any one institute The heat-resistant film stated,
9. a kind of varnish, it includes the polyimide precursor with repeat unit shown in formula (5),
(in formula (5), X1Expression can be by 4 valencys of the carbon number 6~14 that the aromatic series base of carbon number 6~20 substitutes Aromatic series base.)
10. according to 9. varnish, above-mentioned X1For at least one kind of 4 valency group in formula (2)~formula (4),
11. according to 9. or 10. varnish, the inherent viscosity of above-mentioned polyimide precursor is more than 0.3dL/g,
12. a kind of manufacture method of heat-resistant film, it is characterised in that apply the varnish described in 9.~11. any one Cloth is heated on substrate, by it more than 350 DEG C,
13. the polyimide precursor with repeat unit shown in formula (5),
(in formula (5), X1Expression can be by 4 valencys of the carbon number 6~14 that the aromatic series base of carbon number 6~20 substitutes Aromatic series base.)
14. according to 13. polyimide precursor, its inherent viscosity is more than 0.3dL/g.
The effect of invention
The polyimides of the present invention not only has required for the extremely high heat endurance of realization, the dimensional stability of height Low-down coefficient of linear thermal expansion, and have very high glass transition temperature and excellent film toughness concurrently.Therefore, it is of the invention Polyimides be suitable for requiring these characteristics, photo-electric conversion element, light-emitting component, image display device etc. in recent years so Electronic device baseplate material, particularly OLED display plastic substrate material, can aid in the lightweight, crisp of equipment Weak property improves.
Brief description of the drawings
Fig. 1 is the FT-IR spectrum of the polyimide precursor film described in embodiment 1.
Fig. 2 is the FT-IR spectrum of the Kapton described in embodiment 1.
Embodiment
Hereinafter, the present invention is described in detail.
＜ polyimides ＞
The polyimides of the present invention has repeat unit shown in formula (1).
In formula (1), X1Representing can be by the 4 valencys virtue for the carbon number 6~14 that the aromatic series base of carbon number 6~20 substitutes Fragrant race's base.
As the concrete example of 4 valency aromatic series bases of such carbon number 6~14, benzene -1,2 can be enumerated, 4,5- tetra- bases, The bases of benzene -1,2,3,4- four, the bases of naphthalene -1,2,3,4- four, the bases of naphthalene -1,2,5,6- four, the bases of naphthalene -1,2,6,7- four, naphthalene -1,2,7,8- four Base, the bases of naphthalene -2,3,5,6- four, the bases of naphthalene -2,3,6,7- four, the bases of naphthalene -1,4,5,8- four, biphenyl -2,2 ', 3,3 '-four bases, biphenyl - 2,3,3 ', 4 '-four bases, biphenyl -3,3 ', 4,4 '-four bases, the bases of anthracene -1,2,3,4- four, the bases of anthracene -1,2,5,6- four, anthracene -1,2,6, The bases of 7- tetra-, the bases of anthracene -1,2,7,8- four, the bases of anthracene -2,3,6,7- four, the bases of phenanthrene -1,2,3,4- four, the bases of phenanthrene -1,2,5,6- four, phenanthrene -1, The bases of 2,6,7- tetra-, the bases of phenanthrene -1,2,7,8- four, the bases of phenanthrene -1,2,9,10- four, the bases of phenanthrene -2,3,5,6- four, the bases of phenanthrene -2,3,6,7- four, The bases of phenanthrene -2,3,9,10- four, the bases of phenanthrene -3,4,5,6- four, the bases of phenanthrene -3,4,9,10- four, phenyl ether -3,3 ', 4,4 '-four bases, quinhydrones - Base of diphthalic anhydrides-four etc..X in repeat unit1It can be the same or different.
Wherein, X1The preferably bases of benzene -1,2,4,5- four, the bases of naphthalene -1,2,3,4- four, the bases of naphthalene -1,2,5,6- four, naphthalene -1,2, The bases of 6,7- tetra-, the bases of naphthalene -1,2,7,8- four, the bases of naphthalene -2,3,5,6- four, biphenyl -2,2 ', 3,3 '-four bases, biphenyl -2,3,3 ', 4 ' - Four bases, biphenyl -3,3 ', 4,4 '-four bases, more preferably following formula (2)~formula (4) any one.
In the polyimides of the present invention, on the aromatic rings of 4 valency aromatic series bases of the carbon number 6~14 in repetitive structure Any hydrogen atom can be substituted by the aromatic series base of carbon number 6~20.
As the concrete example of the aromatic series base of such carbon number 6~20, phenyl, 1- naphthyls, 2- naphthyls, 1- can be enumerated Anthryl, 2- anthryls, 9- anthryls, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl etc..
＜ polyimide precursors ＞
The polyimides of the present invention can be manufactured by the polyimide precursor with repeat unit shown in following formula (5).
(in formula (5), X1Represent implication same as described above.)
There is the method for the polyimide precursor of repeat unit shown in above-mentioned formula (5) to be not particularly limited for manufacture, Ke Yiying With known method.More specifically, for example, obtaining by the following method.
First, it is the diamines (corresponding with the diamines shown in the formula (6) obtained by aftermentioned method) shown in following formula (8) is molten Solution is slowly added the tetracarboxylic dianhydride shown in following formula (7) in solvent wherein, using mechanical agitator, 0~100 DEG C, it is excellent 20~60 DEG C are elected as to stir 0.5~100 hour, be preferably 1~72 hour.
(in formula (7), X1Represent implication same as described above.)
Now, the diamines shown in formula (8), can relative to diamines 1 with amount of substance (mol) ratio of the acid dianhydride shown in formula (7) Think acid dianhydride 0.8~1.1 or so, preferably 0.9~1.1 or so, more preferably 0.95~1.05 or so.
In addition, the concentration of the monomer (diamines and acid dianhydride) in reaction dissolvent is 5~50 mass %, preferably 10~40 matter Measure %.By being polymerize in the monomer concentration scope, so as to substantially ensure that the dissolubility of monomer and polymer, can obtain Uniformly and the polyimide precursor of high polymerization degree solution.
From the viewpoint of the toughness of the heat-resistant film of the present invention, it is expected that the degree of polymerization of polyimide precursor is as far as possible high, Therefore, it is desirable to make monomer concentration in reaction dissolvent for 5~50 mass %, be preferably 10~40 mass % to modulate polyimides Precursor.
In addition, the degree of polymerization in polyimide precursor excessively increases, polymeric solution becomes in the case of being not easy stirring, also may be used With with reaction used in solvent identical solvent suitably diluted.
In addition, from the viewpoint of the operation of varnish used in the toughness of the heat-resistant film of the present invention and its manufacture, The inherent viscosity of polyimide precursor is preferably more than 0.3dL/g, in the range of more preferably 0.3~5.0dL/g.
From the viewpoint of making heat endurance extremely high as the polyimides performance of object in the present invention such, poly- When closing polyimides, it can be used and be entirely free of the substituent beyond phenyl, the aromatic tetracarboxylic acid two of linker beyond ether Acid anhydride.Even if the use of ester ring type tetrabasic carboxylic acid is a small amount of, it is also possible to heat endurance is significantly damaged, therefore it is not preferred.
As such aromatic tetracarboxylic acid's dianhydride, as long as meeting above-mentioned condition, just it is not particularly limited, equal benzene can be enumerated Tetracarboxylic acid dianhydride, benzene -1,2,3,4- tetracarboxylic acid dianhydrides, naphthalene -1,2,3,4- tetracarboxylic acid dianhydrides, naphthalene -1,2,5,6- tetracarboxylic acid dianhydrides, Naphthalene -1,2,6,7- tetracarboxylic acid dianhydrides, naphthalene -1,2,7,8- tetracarboxylic acid dianhydrides, naphthalene -2,3,5,6- tetracarboxylic acid dianhydrides, naphthalene -2,3,6,7- Tetracarboxylic acid dianhydride, naphthalene -1,4,5,8- tetracarboxylic acid dianhydrides, biphenyl -2,2 ', 3,3 '-tetracarboxylic acid dianhydride, biphenyl -2,3,3 ', 4 '-four Formic acid dianhydride, biphenyl -3,3 ', 4,4 '-tetracarboxylic acid dianhydride, anthracene -1,2,3,4- tetracarboxylic acid dianhydrides, anthracene -1,2,5,6- tetracarboxylic acids two Acid anhydride, anthracene -1,2,6,7- tetracarboxylic acid dianhydrides, anthracene -1,2,7,8- tetracarboxylic acid dianhydrides, anthracene -2,3,6,7- tetracarboxylic acid dianhydrides, phenanthrene -1,2, 3,4- tetracarboxylic acid dianhydrides, phenanthrene -1,2,5,6- tetracarboxylic acid dianhydrides, phenanthrene -1,2,6,7- tetracarboxylic acid dianhydrides, phenanthrene -1,2,7,8- tetracarboxylic acids Dianhydride, phenanthrene -1,2,9,10- tetracarboxylic acid dianhydrides, phenanthrene -2,3,5,6- tetracarboxylic acid dianhydrides, phenanthrene -2,3,6,7- tetracarboxylic acid dianhydrides, phenanthrene -2, 3,9,10- tetracarboxylic acid dianhydrides, phenanthrene -3,4,5,6- tetracarboxylic acid dianhydrides, phenanthrene -3,4,9,10- tetracarboxylic acid dianhydrides, 4,4 '-epoxide two are adjacent Phthalic acid dianhydride, quinhydrones-diphthalic anhydrides etc. are as an example.They can be used alone, can also two or more combination Use.
In above-mentioned aromatic tetracarboxylic acid's dianhydride, in order to obtain the polyimides of the present invention, from exhibiting low thermal expansion characteristics From the viewpoint of such viewpoint and acquisition easiness, cost, preferably using the tetrabasic carboxylic acid with upright and outspoken and straight line structure Dianhydride, i.e. pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,6,7- naphthalenetetracarbacidic acidic dianhydrides are as tetracarboxylic acid Acid dianhydride component.Now, the content of these tetracarboxylic dianhydrides is 50~100 moles of % of whole tetracarboxylic dianhydride's usage amounts, excellent Elect 70~100 moles of % as.
From the viewpoint of the heat endurance extremely high from the polyimides performance of the present invention is such, as above-mentioned formula (8) institute What is illustrated includes benzoThe copolymer composition of the diamines of oxazolyl, can be partly using substituent, the ether being entirely free of beyond phenyl The aromatic diamine of linker beyond base.Wherein, even if the use of ester ring type diamines is a small amount of, it is also possible to significantly infringement heat Stability, thus it is not preferred.
As such aromatic diamine, as long as in the range of above-mentioned condition, just it is not particularly limited, can enumerates to benzene Diamines, m-phenylene diamine (MPD), o-phenylenediamine, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 3,3 '-diaminourea two Double (4- amino-benzene oxygens) benzene of phenyl ether, 2,4 '-diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, benzidine, 1,4-, Double (3- amino-benzene oxygens) benzene of double (4- amino-benzene oxygens) benzene of 1,3-, 1,3-, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, to three Benzidine etc. is as an example.In addition, they may be used alone, two or more kinds can also be used.These copolymerized diamine compositions Usage amount is 0~30 mole of %, preferably 0~10 mole of % of whole diamines usage amounts.
As polymerization the present invention polyimide precursor when used solvent, preferably using DMF, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, dimethyl sulfoxide, 3- methoxyl groups-N, N- dimethylpropane acid amides, 3- are just Butoxy-N, N- dimethylpropane acid amides, 3- sec-butoxies-N, N- dimethylpropane acid amides, 3- tert-butoxies-N, N- dimethyl The non-protonic solvents such as propane acid amides, as long as starting monomer and the dissolving of the polyimide precursor of generation, just have no problem, tied to it Structure is not particularly limited.
It can use for example, the acyl such as DMF, DMA, METHYLPYRROLIDONE The ring-types such as amine solvent, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton The alcohol series solvent of the carbonate solvents such as ester solvent, ethylene carbonate, propylene carbonate, triethylene glycol etc. two, metacresol, paracresol, 3- The phenol series solvents such as chlorophenol, 4- chlorophenols, acetophenone, 1,3- dimethyl-2-imidazolinones, sulfolane, dimethyl sulfoxide etc..
In addition, phenol, orthoresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether, four Hydrogen furans, diethylene glycol dimethyl ether, methyl iso-butyl ketone (MIBK), DIBK, cyclohexanone, methyl ethyl ketone, acetone, butanol, second The in general such as alcohol, dimethylbenzene, toluene, chlorobenzene solvent can also be used partly.
In order to manufacture the polymeric solution that the heat-resistant film of the present invention can directly use the polyimide precursor of the present invention, Be added dropwise, filtered in the poor solvents such as substantial amounts of water, methanol in order to which the heat-resistant film for manufacturing of the invention can also use, Dry and obtain polyimide precursor, it is (molten used in the manufacture of above-mentioned polyimide precursor that it is dissolved in solvent again Agent etc.) obtained by material.In addition, the polymeric solution of above-mentioned polyimide precursor and making polyimide precursor be dissolved in solvent again Obtained by material be all the varnish for including polyimide precursor, be the present invention object.
＜ heat-resistant films (polyimide film) ＞
The heat-resistant film of the present invention can carry out thermal dehydration by the polyimide precursor that will be obtained by the above method Cyclization (imidization reaction) manufactures.
That is, heat-resistant film of the invention is carried out as follows manufacture.
The varnish of polyimide precursor comprising the present invention is cast on the substrates such as glass, copper, aluminium, stainless steel, silicon, It is dried in baking oven at 40~180 DEG C, preferably 50~150 DEG C, makes polyimide precursor film.
As the polyimide precursor film by obtained by substrate in a vacuum, in the non-active gas such as nitrogen or in air Heated to obtain the heat-resistant film (polyimide film) of the present invention.
Now, from the viewpoint of end imidization reaction is such, heating-up temperature is more than 200 DEG C, preferably 250 DEG C More than, from the viewpoint of the thermal decomposition for suppressing generated polyimide film is such, heating-up temperature is less than 450 DEG C, preferably For less than 430 DEG C.
Additionally, it is desirable to imidizate is carried out in a vacuum or in non-active gas, as long as imidizate temperature is not too high, then It can carry out in atmosphere.
In imidization reaction, also can replace heat treatment and by by polyimide precursor film in pyridine, triethylamine etc. In the presence of tertiary amine, it is impregnated in the solution containing the cyclodehydration reagent such as acetic anhydride to carry out.
It is further possible to these cyclodehydration reagents are put into the varnish comprising polyimide precursor in advance at room temperature Middle stirring, it is cast on aforesaid substrate, dried, so as to make the polyimide precursor of partly imidizate Film, by the way that it to be further made as above to heat treatment, polyimide film can be obtained.
By the way that the varnish of the polyimide precursor comprising the present invention is coated on into metal foil, is dried on such as copper foil Afterwards, imidizate is carried out using above-mentioned condition, it is hereby achieved that the laminated body of metal level and polyimide film.Then chlorine is used Change the etching solutions such as water solution by etching metal layer into desired circuit shape, so as to manufacture non-binding formulation flexible printing Substrate.
The thickness of the heat-resistant film of the present invention is not particularly limited, as long as suitably determining thickness i.e. according to application target Can, if using the heat-resistant film in itself as photo-electric conversion element as organic solar batteries, silicon solar cell, have In the case of the substrate use of light-emitting component, electric circuit electronics technical as machine EL element, 1~100 μm or so is suitable.
The heat-resistant film of present invention mentioned above can be by the polyamides with excellent film Forming ability of the present invention The precursor of imines easily manufactures, and has the low thermal expansion characteristics of extremely high VOC rejection abilities and height, therefore can be adapted to The film of heat resistance in substrate as organic EL element, liquid crystal display cells, organic solar batteries etc..
＜ includes benzoThe synthesis ＞ of the diamines (hereinafter also referred to as the diamines containing BO) of oxazolyl
The present invention polyimide precursor and polyimides as described above, by be used as monomer tetracarboxylic dianhydride and Diamines containing BO obtains.
Diamines used in the present invention containing BO bases is represented with following formula (8).
The diamines containing BO bases shown in above-mentioned formula (8) uses double (o-aminophenols) shown in following formula (9) to be used as Beginning raw material synthesizes.
Hereinafter, on having used 3,3 '-dihydroxybiphenyl amine (hereinafter referred to as p-HAB.) as double (o-aminophenols) In the case of the diamines containing BO bases synthetic method, one 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 being dehydrated well, adds pyrrole wherein Pyridine is sealed A liquid is made as deacidification agent with dottle pin lid.
Next, in eggplant type flask, the 4- nitrobenzoyl chlorides of p-HAB 2 times of moles are dissolved in same with A liquid Solvent, sealed with dottle pin lid B liquid is made.
And then cooled down A liquid in ice bath, while being stirred using rotor while using syringe that B liquid is every Secondary a small amount of gradation is added in A liquid, and addition continues to stir a few hours after terminating, and synthesizes diamides body.
Next, remove ice bath, after a few hours are stirred at room temperature, in order that cyclodehydration reaction terminate and in the reaction The p-methyl benzenesulfonic acid of appropriate amount is added in solution, a few hours backflow is carried out using 200 DEG C of oil baths.
The sediment of generation is collected by filtration, after being washed repeatedly with water, is dried in vacuo 12 hours, synthesizes at 100 DEG C 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, addition is suitable The Pd/C of equivalent carries out 1~24 hour reduction reaction in hydrogen atmosphere as catalyst in room temperature~150 DEG C.Reaction is entered Row can be tracked by thin-layer chromatography.
After reaction terminates, after Pd/C is isolated by filtration out, filtrate is added dropwise in a large amount of water at leisure analyses product Go out.Sediment is collected by filtration, after being washed repeatedly with water, is dried in vacuo 12 hours at 100 DEG C.Can also be as needed from suitable When solvent recrystallized and carry out high purity.
So, it can obtain and contain BO shown in the following formula (6) for the polymerization that can be used for the polyimide precursor of the present invention The diamines of base.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to these embodiments.In addition, with Physics value in lower example is measured by the following method.
＜ infrared absorption spectroscopies ＞
Using fourier-transform infrared spectrophotometer (Japan light splitting society FT-IR5300), contained using KBr plates method measure There is the infrared absorption spectrum of the diamines of BO bases.Polyimide precursor film and polyimide film (about 5 are determined also with penetrant method μ m-thick) infrared absorption spectrum.
＜1H-NMR spectrum ＞
Using society of JEOL NMR spectrophotometers (ECP400), measure contains BO bases in deuterated dimethylsulfoxide Diamines1H-NMR spectrum.
＜ differential scanning calorimetric analysis (fusing point and fusion curve) ＞
Using Block ル カ ー エ イ エ ッ Network ス society's differential scanning calorimetric analysis devices (DSC3100), in nitrogen atmosphere With the fusing point and fusion curve of the 2 DEG C/min of diamines of measure containing BO bases of programming rate.Fusing point is higher, and melting peak is more sharp, table Show that purity is higher.
＜ inherent viscosities ＞
It is measured using Ostwald viscometer in 30 DEG C of polyimide precursor solutions to 0.5 mass %.
＜ glass transition temperatures (Tg) ＞
Mechanical analytical equipment (TMA4000) is heated using Block Le カ ー エ イ エ ッ Network ス societies, is surveyed by dynamic viscoelastic It is fixed, polyimide film (20 μ m-thick) is obtained by the peak temperature of off-energy curve when frequency 0.1Hz, 5 DEG C/min of programming rate Glass transition temperature.
＜ coefficients of linear thermal expansion：CTE ＞
Mechanical analytical equipment (TMA4000) is heated using Block Le カ ー エ イ エ ッ Network ス societies, by thermo-mechanical analysis, by The elongation of test film when 1 μm of loading 0.5g/ thickness, 5 DEG C/min of programming rate, as being averaged for 100~200 DEG C of scopes Value obtains the CTE of polyimide film (20 μ m-thick).
The weight of ＜ 5% reduces temperature (Td 5) ＞
Using Block Le カ ー エ イ エ ッ Network ス society's thermogravimetry devices (TG-DTA2000), in nitrogen or air In with the temperature-rise period of 10 DEG C/min of programming rate, when the initial weight of measure polyimide film (20 μ m-thick) reduces 5% Temperature.These values are higher, represent that heat endurance is higher.
＜ modulus of elasticity, elongation at break, fracture strength ＞
Using ボ ー Le ドウィン societies of Japan cupping machine (テ Application シ ロ Application UTM-2), to polyimides test film (3mm × 30mm × 20 μ m-thick) implements tension test (draw speed：8mm/ minutes), by the Initial Gradient for answering force-strain curve Modulus of elasticity is obtained, elongation when being broken by film obtains elongation at break (%).Elongation at break is higher, it is meant that film it is tough Property is higher.
[synthesis example 1]
＜ contains the synthesis ＞ of the diamines of BO bases
In 3 mouthfuls of flasks, p-HAB (Wakayama refine society's system, 2.61g, 12mmol) is dissolved in what is be dehydrated well METHYLPYRROLIDONE (hereinafter referred to as NMP.) in (81mL), add pyridine (2.9mL, 36mmol) wherein and be used as depickling Agent, sealed with dottle pin lid A liquid is made.Next in another eggplant type flask, by 4- nitrobenzoyl chlorides (4.49g, NMP (17mL) 24mmol) is dissolved in, is sealed with dottle pin lid B liquid is made.A liquid is cooled down in ice bath, a lateral dominance It is stirred with rotor while by B liquid, a small amount of gradation is added in A liquid every time using syringe, addition continues stirring 3 after terminating Hour, synthesize diamides body.
Next remove ice bath, after a few hours are stirred at room temperature, in order that cyclodehydration reaction terminate and in the reaction The p-methyl benzenesulfonic acid (1.90g, 11mmol) of appropriate amount is added in solution, using 200 DEG C of oil baths flow back within 3 hours.Pass through The sediment of generation is recovered by filtration, is washed with water.Now, wash repeatedly until being properly added 1% silver nitrate in washing lotion The aqueous solution does not also observe white precipitate, completely removes chlorion.Then after being washed with ethanol, done in 100 DEG C of vacuum Dry 12 hours, the yellow needles that 401 DEG C of fusing point is obtained with yield 81% were brilliant.
The product of gained is in DMSO-d6、CDCl3In it is almost insoluble, therefore be not carried out1H-NMR is determined, but infrared at its In line absorption spectrum, in 1605cm-1BO base C=N stretching vibration bands are shown, in 1518/1348cm-1Show nitro stretching vibration Band, acid amides C=O stretching vibration bands, phenol O-H stretching vibration bands are not observed.
According to these results, it is believed that the product of gained is the dinitro matrix shown in following formula (10).
Next, in 3 mouthfuls of flasks, the dinitro matrix (6.13g, 11.9mmol) shown in above-mentioned formula (10) is dissolved in In NMP (250mL), addition Pd/C (0.63g) is used as catalyst, and 15 hours reduction reactions are carried out at 100 DEG C in hydrogen atmosphere. Reaction be tracked by thin-layer chromatography.After reaction terminates, after Pd/C is isolated by filtration out, filtrate is dripped at leisure Adding in substantial amounts of water separates out product.Sediment is recovered by filtration, after being washed repeatedly with water, in 100 DEG C of vacuum drying 12 hours, brown powder is obtained with thick product yield 82%.In addition, in order to improve purity, tied again from gamma-butyrolacton Crystalline substance, it is finally brilliant in 100 DEG C of brown tabulars for being dried in vacuo 12 hours and obtaining 354 DEG C of fusing point.
In the infrared absorption spectrum of the product of gained, in 3454/3380/3210cm-1Show amino N-H stretching vibrations Band, in 1621/1607cm-1BO base C=N stretching vibration bands are shown, in 1499cm-1Isosorbide-5-Nitrae-phenylene stretching vibration band is shown, not It was observed that nitro stretching vibration band, acid amides C=O stretching vibration bands.
By the result of the infrared absorption spectrum and following1H-NMR spectrum and the results verification of elementary analysis, gained Product be the diamines containing BO bases shown in following formula (6).
1H-NMR spectrum (400MHz, DMSO-d6, 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)
Elementary analysis：Presumed value C；74.63%, H；4.34%, N；13.39%, assay value C；74.41%, H；4.47%, N；13.26%
The evaluating characteristics ＞ of the polymerizations of ＜ polyimide precursors, imidizate and polyimide film
[embodiment 1]
Added in the closed reaction vessel with mixer dried well shown in above-mentioned formula (6) containing BO bases Diamines 5mmol, in the NMP being fully dehydrated with molecular sieve 4A after about 50 DEG C are dissolved, let cool to room temperature, it is molten at this 2,3,6 are added in liquid, (total soluble matters is dense by powder 5mmol for 7 '-naphthalenetetracarbacidic acidic dianhydride (JFE ケ ミ カ Le society system, hereinafter referred to as NTDA) Degree：13 mass %).Then, it is stirred at room temperature 72 hours, obtains the uniform and sticky solution for including polyimide precursor (polyimide precursor solution).
It is sub- in the polyamides that 30 DEG C of concentration with 0.5 mass % determine to obtain using Ostwald viscometer in NMP The inherent viscosity of amine precursor is 1.15dL/g.
Above-mentioned polyimide precursor solution is coated on glass substrate, dried 3 hours at 80 DEG C in air drier, system Make polyimide precursor film.
The infrared absorption spectrum of the film for the polyimide precursor that Fig. 1 displays obtain.In 2600cm-1Nearby observe width Absorption band (hydrogen bond COOH base O-H stretching vibration bands), in 1711cm-1Observe hydrogen bond COOH base C=O stretching vibrations Band, in 1678cm-1(shoulder)/1530cm-1Amide groups C=O stretching vibration bands are observed, in 1501cm-1Observe 1,4- Asias benzene Base stretching vibration band, on the other hand, have no amino N-H stretching vibration bands from monomer, the anhydride group C=of tetracarboxylic dianhydride O stretching vibration bands, therefore confirm to generate the polyimide precursor of target.
Then, by polyimide precursor film together with glass substrate 250 DEG C heat 1 hour, further in a vacuum 1 hour is heated to carry out hot-imide at 350 DEG C, is then peeled to remove residual stress from substrate, further true Carry out being heat-treated for 1 hour at 400 DEG C in the air, obtain the soft polyimide film of 20 μm of thickness.
Fig. 2 is shown in the infrared absorption spectrum of the polyimide film separately made under identical conditions.In 3046cm-1Observation To aromatic series C-H stretching vibration bands, in 1777/1721cm-1Imide C=O stretching vibration bands are observed, in 1618cm-1See BO base C=N stretching vibration bands are measured, in 1501cm-1Isosorbide-5-Nitrae-phenylene stretching vibration band is observed, in 1356cm-1Observe acyl Imido grpup N-C (aromatic series) stretching vibration band, on the other hand, the absorption band from COOH bases, amide groups is had no, therefore confirm Imidization reaction finishes, and generates the polyimides of target.
The polyimide film of gained does not all show dissolubility completely for any organic solvent.To polyimide film (thickness 20 μm) carry out Measurement of Dynamic Viscoelasticity obtain as a result, observing glass transition point at 408 DEG C.Coefficient of linear thermal expansion shows Show value extremely low as 8.4ppm/K.It is considered that this is due to that the backbone structure of the polyimides of the present invention is extremely upright and outspoken And linearity is high, therefore polyimides main chain is significantly orientated in the direction parallel with film surface in hot-imide process. It is 603 DEG C that 5% weight, which reduces temperature in nitrogen, is in atmosphere 592 DEG C, it is known that the polyimides of gained has extremely high Heat endurance.Further evaluation mechanical property obtain as a result, tensile modulus of elasticity (Young's modulus) is 3.8GPa, fracture is stretched Long rate is 39%, also maintains excellent film toughness.Physics value is concluded in table 1.
[embodiment 2]
As tetracarboxylic dianhydride's composition, instead of NTDA using with the 3 of mole, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (and Guang Chun medicines society system, hereinafter referred to as BPDA), in addition, before polymerizeing polyimides according to the method described in embodiment 1 Body, it is filmed, hot-imide, film evaluation of physical property.Physical property is shown in table 1.It is same with the polyimides described in embodiment 1 Ground shows excellent characteristic.
In addition, in table, ND represents to be not detected by glass transition in the Measurement of Dynamic Viscoelasticity of room temperature~500 DEG C.
[embodiment 3]
As tetracarboxylic dianhydride's composition, pyromellitic acid anhydride (Mitsubishi's gas with mole is used instead of NTDA Learn society's system, hereinafter referred to as PMDA), in addition, it polymerize polyimide precursor according to the method described in embodiment 1, carries out Film, hot-imide, film evaluation of physical property.Physical property is shown in table 1.Shown in the same manner as the polyimides described in embodiment 1 Excellent characteristic.
[comparative example 1]
The PMDA of same mole is used as tetracarboxylic dianhydride's composition, as diamine component use same mole to benzene two Amine, it is polymerize according to the method described in embodiment 1, is film-made, hot-imide, producing polyimide film.The polyamides is sub- Amine film shows extremely low CTE (2.8ppm/K), but fragile in the extreme, elongation at break 0%.In addition, the film easily due to Bend and be broken.Because coming from the bar-shaped backbone structure of the polyimides system, the winding between polymer chain does not almost have.
[comparative example 2]
The PMDA of same mole is used as tetracarboxylic dianhydride's composition, the 4 of same mole, 4 ' are used as diamine component- Epoxide diphenylamines, it is polymerize according to the method described in embodiment 1, is film-made, hot-imide, film evaluation of physical property.The polyamides Imines film shows extremely high glass transition temperature (408 DEG C), has the excellent toughness of elongation at break 85%, but CTE is 42.8ppm/K, low thermal expansion characteristics are not shown.
[table 1]

Claims (5)

1. a kind of manufacture method of heat-resistant film, it is characterised in that be coated on the varnish containing following polyimide precursors On substrate, it is set to be heated more than 350 DEG C,
The polyimide precursor is as containing benzo shown in tetracarboxylic dianhydride and following formula (8)The diamines of oxazolyl obtains The polyimide precursor with repeat unit shown in following formula (5),
In formula (5), X1For 4 valency groups shown in formula (4),
2. the manufacture method of heat-resistant film according to claim 1, the inherent viscosity of the varnish for 0.3dL/g with On.
3. a kind of heat-resistant film, it is obtained as the manufacture method described in claim 1.
4. heat-resistant film according to claim 3, thickness is 1~100 μm.
5. the substrate of a kind of photo-electric conversion element, light-emitting component or electronic circuit, it includes resistance to described in claim 3 or 4 Hot film.
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