CN107614495A - Tetracarboxylic dianhydride, polyamic acid and polyimides with ring-type hydrocarbon skeleton and ester group - Google Patents
Tetracarboxylic dianhydride, polyamic acid and polyimides with ring-type hydrocarbon skeleton and ester group Download PDFInfo
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- CN107614495A CN107614495A CN201680030038.0A CN201680030038A CN107614495A CN 107614495 A CN107614495 A CN 107614495A CN 201680030038 A CN201680030038 A CN 201680030038A CN 107614495 A CN107614495 A CN 107614495A
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- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
By polyimides represented with following formula (1) while with the tetracarboxylic dianhydride of ring-type hydrocarbon skeleton and ester group manufacture with excellent solvent soluble, low-dielectric, the transparency.[changing 1]Wherein, x represents 1~11 integer, R1And R2The aromatic series base of the alkyl of expression carbon number 1~12, halogen atom, hydroxyl, the cycloalkyl of carbon number 4~16 or carbon number 6~12 independently of one another.Multiple R be present1And/or R2In the case of, each group can be with identical or different.M and n separately represents 0 or 1~4 integer.
Description
Technical field
One kind used the present invention relates to the raw material that can be used as polyimide resin etc., that there is ring-type hydrocarbon skeleton and ester group
New tetracarboxylic dianhydride and polyamic acid, the polyimides using the tetracarboxylic dianhydride.
Background technology
Tetracarboxylic dianhydride except as epoxy resin, polyurethane resin curing agent in addition to, also as polyimide resin
Raw material use.Especially, polyimides is in addition to excellent heat resistance, also with mechanical property, electrical characteristic,
Chemical proofing, in electric and electronic material, the particularly field of semiconductor electronic material, it is used as flexibility extensively
Printed circuit board (PCB), interlayer dielectric and diaphragm.But most polyimides does not dissolve in organic solvent, polyimides sheet
Body is generally not easy to form.Therefore, polyimides is utilized for being shaped to film etc. for the polyamic acid solution of precursor,
250~350 DEG C are waited progress thermal dehydration closed loop (imidizate) processing under high temperature.But with the densification of electronic circuit,
The problem of being brought using multilayer circuit board be, by polyimides/metal substrate laminate from hot-imide temperature (250~350
DEG C) be cooled to room temperature during caused thermal stress often cause warpage, the stripping of film, problems of crack, cause device
Reliability the problem of being remarkably decreased.
On the other hand, it is sub- only by polyamides is coated with metallic substrates if polyimides dissolves in organic solvent
The solvent solution (varnish) of amine, evaporation drying solvent is plastic at a temperature of less than hot-imide temperature, its result
It is that can reduce the thermal stress in polyimides/metal substrate laminate, therefore, it is intended that obtaining the polyamides Asia for dissolving in solvent
Amine.
Also, for the processing speed of the devices such as LSI (large scale integrated circuit), it is desirable to be able to realize further high speed
Change.One of method for realizing the high speed is periphery to be connected up with the interlayer dielectric cladding of low dielectric constant, as the interlayer
The polyimides of excellent heat resistance can be used in dielectric film, and still, the dielectric constant of typical polyimides is 3.5~3.0, this area
In want to further reduce dielectric constant.
Further, in recent years, it is heat-resisting for being used in the fiber waveguide proposed as the surface installation base plate of a new generation
Property polyimides good and that the transparency is high studied, if it is possible to obtain having concurrently high transparency and heat resistance, solubility,
The polyimides of the toughness of appropriateness, then its will can act as the glass that is used in LCDs, Electronic Paper, solar cell etc.
Glass substrate replaces material.
As with such solvent soluble, low-dielectric, high transparency high-fire resistance polyimides, for example,
Know the polyimides manufactured by the amine such as the tetracarboxylic dianhydride with ester bond and 4,4 '-oxygen diphenylamines (4,4 '-ODA), wherein institute
The tetracarboxylic dianhydride with ester bond is stated by double (4- hydroxy phenyls) Fluorenone manufactures (patent document 1) of 9,9-.But, it is still desirable to obtain
Obtain and further improve solvent soluble, low-dielectric, the polyimides of the transparency.
[prior art literature]
[patent document]
[patent document 1] Japanese Laid-Open Patent Publication Laid-Open 2007-91701 publications
The content of the invention
[technical problem that invention solves]
It is an object of the present invention to provide one kind to have low-dielectric, high transparency and the deliquescent polyamides of high solvent sub-
Amine.
[means for solving technical problem]
Inventor is conceived to the research that the structure of the tetracarboxylic dianhydride among the raw material of polyimides is made great efforts, as a result
It was found that by making that there is the tetracarboxylic dianhydride of ring-type hydrocarbon skeleton and ester group to obtain polyimides with diamines Type of Collective simultaneously, can
Manufacture has the features such as low-dielectric, high transparency, and the polyamides for having the features such as dissolubility height in organic solvent concurrently is sub-
Amine, so as to complete the present invention.That is, the invention provides the technical scheme of following (1)~(3).
(1) tetracarboxylic dianhydride represented by following formula (1),
[changing 1]
Wherein, x represents 1~11 integer, R1And R2Represent independently of one another the alkyl of carbon number 1~12, halogen atom, hydroxyl,
The cycloalkyl of carbon number 4~16 or the aromatic series base of carbon number 6~12.Multiple R be present1And/or R2In the case of, each group can
With identical or different.M and n represents 0 or 1~4 integer independently of one another.
(2) there is the polyamic acid of the repeat unit represented by following formula (2),
[changing 2]
Wherein, x, R1、R2, m and n it is as defined above.Also, Z represents diamines residue.
(3) there is the polyimides of the repeat unit represented by following formula (3),
[changing 3]
Wherein, x, R1、R2, m, n and Z it is as defined above.
[The effect of invention]
According to it is a discovery of the invention that by simultaneously will there is the tetracarboxylic dianhydride of ring-type hydrocarbon skeleton and ester group to be birdsed of the same feather flock together with diamines
Close, can manufacture with features such as low-dielectric, high transparency, and have the features such as dissolubility height in organic solvent concurrently
Polyimides.The polyimides has the features such as low-dielectric, high transparency and dissolubility height in organic solvent, therefore energy concurrently
The electronic materials such as the interlayer dielectric of flexible print wiring board, the diaphragm of semiconductor element, integrated circuit are enough suitable as, with
And the optic communication material such as optical fiber, fiber waveguide, instead of conventional use of in LCDs, Electronic Paper, solar cell etc.
The purposes such as the flexible substrate of glass substrate.
Brief description of the drawings
Fig. 1 is the tetrabasic carboxylic acid two with the structure represented by following formula (1-A) among the tetracarboxylic dianhydride represented by above formula (1)
Acid anhydride1H-NMR is composed.
Fig. 2 is the tetrabasic carboxylic acid two with the structure represented by following formula (1-A) among the tetracarboxylic dianhydride represented by above formula (1)
Acid anhydride13C-NMR is composed.
Fig. 3 is the tetrabasic carboxylic acid two with the structure represented by following formula (1-A) among the tetracarboxylic dianhydride represented by above formula (1)
The mass spectrogram of acid anhydride.
Embodiment
The tetracarboxylic dianhydride ＞ containing ring-type hydrocarbon skeleton and ester group new ＜
The present invention and its embodiment are recorded below.The tetracarboxylic acid containing ring-type hydrocarbon skeleton and ester group in present invention
Acid dianhydride is represented by following formula (1).
[changing 4]
Wherein, x represents 1~11 integer, R1And R2Represent independently of one another the alkyl of carbon number 1~12, halogen atom, hydroxyl,
The cycloalkyl of carbon number 4~16 or the aromatic series base of carbon number 6~12.Multiple R be present1And/or R2In the case of, each group can
With identical or different.M and n represents 0 or 1~4 integer independently of one another.
By above formula (1) represent chemical constitution among, represent ring-type hydrocarbon skeleton alkylene radix x be 1~11 integer.
Specifically, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl, ring tridecyl, the ring tetradecane are represented
Base, cyclopentadecane base, ring cetyl, ring heptadecyl, ring octadecyl.For the acquired angle of raw material, preferably
Be cyclooctyl, cyclodecyl, cyclo-dodecyl, more preferably cyclopentadecane base, cyclo-dodecyl.
In above formula (1), as R1And R2The alkyl of middle carbon number 1~12, it can enumerate for example, methyl, ethyl, n-propyl, different
The straight-chains such as propyl group, normal-butyl, sec-butyl, the tert-butyl group, amyl group, hexyl or branched alkyl.As the alkyl of carbon number 1~12,
The preferably straight-chain of carbon number 1~8 or branched alkyl, the more preferably straight-chain of carbon number 1~6 or branched alkyl, enter one
Step is preferably the straight-chain of carbon number 1~3 or branched alkyl.As the cycloalkyl of carbon number 4~16, can enumerate for example, cyclopenta,
Cyclohexyl, the cyclopenta of alkyl (for example, alkyl of carbon number 1~4) substitution, alkyl (for example, alkyl of carbon number 1~4) substitute
The cycloalkyl or alkyl-substituted cycloalkyl of the carbon numbers such as cyclohexyl 4~16 (being preferably carbon number 5~8).Cycloalkyl is preferably ring penta
Base or cyclohexyl.As the aromatic series base of carbon number 6~12, can enumerate for example, phenyl, alkyl (for example, alkyl of carbon number 1~4)
Substituted phenyl, naphthyl.Aromatic series base is preferably phenyl or alkyl-substituted phenyl (for example, tolyl, xylyl, ethylbenzene
Base etc.), more preferably phenyl.As halogen atom, the examples such as fluorine, chlorine, bromine, preferably chlorine or bromine can be enumerated.
The substituent R represented with m and n1And R2Number be 0 or 1~4 integer, preferably 0,1 or 2.M and n can phase
It is same or different, but typically identical.
On the R in above formula (1) described in detail above1And R2, from the cyclic hydrocarbon chemical combination represented by following formula (4) as raw material
For the acquired angle of thing, in these substituents, substituent number is 1 (m=n=1), and the substituent is methyl, second
The compound of base, phenyl；Substituent number is 2 (m=n=2), the compound of all methyl of the substituent；Or do not take
Dai Ji, i.e. m=n=0 compound are preferable, and especially, substituent number is 1, and the substituent is the compound of methyl
Or the compound of no substituent is preferable.
The tetracarboxylic dianhydride represented by above-mentioned formula (1) serves not only as polyimides raw material and used, and is also used as polyester
Deng resin raw material, additive or epoxy resin, the curing agent etc. of polyurethane resin.
The manufacture method ＞ for the tetracarboxylic dianhydride that ＜ is represented by above-mentioned formula (1)
In the present invention, the method as the tetracarboxylic dianhydride for obtaining being represented by above-mentioned formula (1), can suitably be applicable
Known method.It can enumerate for example, in the presence of deoxidier (alkali), make by following formula (4)
[changing 5]
(wherein, x, R1、R2, m and n it is as defined above.)
Double (4- hydroxy phenyls) naphthenics (hereinafter also referred to bis-phenol naphthenic) of the 1,1- of expression and trimellitic anhydride
The method (sour halide) that acid halide reacts；Make by the bis-phenol naphthenic that above-mentioned formula (4) represents and inclined benzene front three
The method of Direct Dehydration reaction occurs between acid anhydrides；Make the diacetate esters by the bis-phenol naphthenic of above-mentioned formula (4) expression and inclined benzene
The method that desacetoxy reaction occurs at high temperature for front three acid anhydrides；Using dehydrating agents such as dicyclohexylcarbodiimides, make by above-mentioned formula
(4) method of dehydrating condensation occurs with trimellitic anhydride for the bis-phenol naphthenic represented；Use paratoluensulfonyl chloride/N, N- diformazans
, will be by the bis-phenol naphthenic esterification that above-mentioned formula (4) represents after base formamide/pyridine mixtures activate trimellitic anhydride
Method.Wherein, due to can be cheap as the halide of the trimellitic acid of raw material in acid halide method acquisition, therefore
Acid halide method is preferable.Hereinafter, acid halide method is described in detail.
So-called acid halide method, is referred specifically to, and in the presence of deoxidier, makes the bis-phenol represented by above-mentioned formula (4)
The acid halide of trimellitic anhydride of the naphthenic with being represented by following formula (7) reacts, and obtains being represented by above-mentioned formula (1)
Tetracarboxylic dianhydride reaction (following, this reaction also referred to as esterification).In addition, the bis-phenol ring represented by above-mentioned formula (4)
Alkanes corresponds to the ring-type hydrocarbon skeleton of the tetracarboxylic dianhydride represented by above-mentioned formula (1).
Commercially available product can be used as the bis-phenol naphthenic represented by above-mentioned formula (4) that raw material uses, can also be by
The method known is (for example, Japanese Laid-Open Patent Publication 2010-248164 publications, Japanese Laid-Open Patent Publication 2011-
6337 publications etc.) manufacture., specifically, can be by the mercaptan that uses in acid catalyst and if necessary as the manufacture method
Under the coexisting of class, make by following formula (5)
[changing 6]
(wherein, x is as defined above.)
The cyclic ketones class of expression with by following formula (6)
[changing 7]
(wherein, R3Represent independently of one another the alkyl of carbon number 1~12, halogen atom, hydroxyl, carbon number 4~16 cycloalkyl or
The aromatic series base of carbon number 6~12.Multiple R be present3In the case of, each group can be with identical or different.K represents 0 or 1~4
Integer.)
The phenols of expression reacts and obtained.In addition, the phenols represented by above-mentioned formula (6) can also mix when necessary
Use two or more.
Acid halide for the trimellitic anhydride of esterification has by following formula (7)
[changing 8]
(Y is halogen atom.)
The structure of expression.The acid chloride of trimellitic anhydride can be obtained inexpensively, therefore Y is preferably chlorine atom.
On the dosage of the acid halide of the trimellitic anhydride represented by above-mentioned formula (7) for esterification, lead to
Often, relative to 1 mole of the bis-phenol naphthenic represented by above-mentioned formula (4), using 2~4 times of mole, preferably using 2.2~2.6
Times mole.When the dosage of the acid halide of trimellitic anhydride is less than 2 times of moles, reaction sometimes can not be fully
Carry out.When more than 4 times of moles, it can be remained in as impurity in system, may result in obtain is represented by above-mentioned formula (1)
Tetracarboxylic dianhydride purity decline.
As the deoxidier for esterification, can enumerate for example, pyridine, triethylamine, DMA etc. are organic
The inorganic bases such as the epoxies such as tertiary amines, expoxy propane, allyl glycidyl ether, potassium carbonate, sodium hydroxide.These deoxidiers can
To use a kind, or and two or more can also be used when necessary.In these deoxidiers, from manufacturing cost and the appearance of separation
For the angle of easy property, pyridine suitably uses.As the dosage of deoxidier, relative to the bis-phenol represented by above-mentioned formula (4)
1 mole of naphthenic, usually 2~4 times of moles, preferably 2~3 times of moles.By making the dosage of deoxidier be 2 times moles
More than amount, it is possible to increase reaction speed；Below 4 times of moles, then it can suppress the generation of impurity.
When implementing esterification, organic solvent can be used when necessary.As the organic solvent that can be used, can lift
Go out for example, the ketone solvent such as acetone, MEK, methylisobutylketone, 1,2- dimethoxy-ethane, tetrahydrofuran, cyclohexyl methyl ether etc.
Ether solvents, benzene,toluene,xylene etc. are aromatic hydrocarbon, the halogenated aromatic such as chlorobenzene, dichloro-benzenes.Preferably ether solvents.Using
In the case of organic solvent, generally, relative to the times of weight of bis-phenol naphthenic 1 represented by above-mentioned formula (4), 1~30 weight is used
Times, preferably using 1~5 times of weight.These organic solvents can use a kind, or be mixed with two or more when necessary.
Reaction temperature during esterification is usually -10 DEG C~110 DEG C, is preferably -5 DEG C~80 DEG C, more preferably 20 DEG C
~70 DEG C.If reaction temperature is higher than 110 DEG C, accessory substance may increase；If reaction temperature is less than -10 DEG C, reacting may nothing
Method is effectively carried out.
As the method for esterification, for example, can be implemented by following steps：In the inclined benzene three represented by above-mentioned formula (7)
In the mixed solution of the acid halide of formic anhydride and above-mentioned organic solvent, while stirring the solution, side is intermittently or continuously added
The solution obtained in above-mentioned solvent is blended in by the bis-phenol naphthenic and deoxidier that are represented by above-mentioned formula (4), to reach above-mentioned
Range of reaction temperature, after addition, further reacted in the range of said temperature.
After esterification terminates, crystallization is separated out by the way that reaction mass is cooled into 15~35 DEG C, the crystallization of precipitation is filtered
Separation, obtain the tetracarboxylic dianhydride represented by above-mentioned formula (1) of the present invention.The obtained tetrabasic carboxylic acid two represented by above-mentioned formula (1)
The conventional purification operations such as adsorption treatment, recrystallization or distillation can also be repeated in acid anhydride when necessary.
Also, after esterification terminates, into reaction mass adding water and organic solvent is washed, it is of the invention by
The tetracarboxylic dianhydride that above-mentioned formula (1) represents is extracted into organic solvent layer, removes containing excessive deoxidier and trimellitic acid
After the water layer of the acid halide of acid anhydride and the halide salt of deoxidier, further, it can also make to make in the water-washing step
The open loop body (the hydrolyzable thing of the tetracarboxylic dianhydride represented by above-mentioned formula (1)) generated for accessory substance is in organic solvent and acetic acid
Ring-closure reaction occurs in the presence of acid anhydride, regenerates the tetracarboxylic dianhydride represented by above-mentioned formula (1), is then similarly tied through separating out
Crystalline substance is separated by filtration, and obtains the tetracarboxylic dianhydride of above-mentioned formula (1) expression.The obtained tetracarboxylic dianhydride represented by above-mentioned formula (1)
Conventional purification operations can also be repeated same as mentioned abovely.
On the purity of the tetracarboxylic dianhydride represented by above-mentioned formula (1), from being easy to improve the polyamides represented by above-mentioned formula (2)
For the angle of the degree of polymerization of amino acid or the polyimides represented by above-mentioned formula (3), generally, the HPLC determined with method described later
Purity is more than 95%, preferably more than 99%.
＜ has the polyamic acid and its manufacture method ＞ of the repeat unit represented by above-mentioned formula (2)
Next, to the polyamic acid with the repeat unit represented by above-mentioned formula (2) (hereinafter also referred to as the present invention's
Polyamic acid) it is described in detail.The polyamic acid of the present invention has the repeat unit represented by following formula (2).
[changing 9]
(wherein, x, R1、R2, m and n it is as defined above.Also, Z represents diamines residue.)
Also, diamines residue described in above-mentioned formula (2) is referred in the tetracarboxylic dianhydride represented by above-mentioned formula (1) with after
It is being obtained during the Diamines reaction stated, diamines to remove amino (- NH2) beyond structure.
On the molecular weight of the polyamic acid of the present invention, the molecular weight obtained by assay method described later is with Weight-average molecular
Amount is calculated as 10,000 above is preferable, and 20,000 above is it is furthermore preferred that 40,000 above is it is further preferred that also, less than 600,000 be
Preferably, less than 500,000 be it is furthermore preferred that less than 300,000 be further preferred.If the molecular weight of polyamic acid is more than 10,000,
It can then be molded, and be easy to keep good mechanical characteristic.If in addition, the molecular weight of polyamic acid be less than 600,000, it is more
In the case of number, easily controllable molecular weight during synthesis, and the appropriate solution of viscosity is readily obtained, easily handled.It is also, poly-
The viscosity of acid amides acid solution can reflect the molecular weight of polyamic acid.
As the manufacture method of the polyamic acid of the present invention, for example, it is molten that Diamines described later are dissolved in into polymerization described later
After in agent, the powder of the tetracarboxylic dianhydride represented by above-mentioned formula (1) of the present invention is added generally at 10~20 DEG C, then,
Stirred at 10~100 DEG C, preferably 10~30 DEG C, so as to obtain the polyamic acid of the form of the solution of polymer solvent (with
Under, also referred to as polyamic acid solution).
As the diamines that can be used in the present invention, as long as belonging to the polymerisation of unobvious infringement polyimide precursor
Property, polyimides requirement performance scope, then there is no particular limitation, can use conventional aromatic diamine, aliphatic
Diamines, ester ring type diamines etc..As such diamines, can enumerate for example, Isosorbide-5-Nitrae-diaminobenzene, 1,3- diaminobenzenes, 2,4- bis-
Amino toluene, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether (alias 4,4 '-oxygen diphenylamines), 3,3 '-two
Aminodiphenyl base sulfone, 3,4 '-diamino-diphenyl ether, 3,3 '-dimethyl -4,4 '-benzidine, 2,2 '-dimethyl -4,
4 '-benzidine, 2,2 '-bis- (trifluoromethyls) -4,4 '-benzidines (alias 2,2 '-bis- (trifluoromethyl) benzidine),
3,7- diaminourea-dimethyl Dibenzothiophene -5,5- dioxide, 4,4 '-diaminobenzophenone, 3,3 '-diaminourea hexichol
Ketone, 4,4 '-bis- (4- aminophenyls) thioethers, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminobenzene formailide, 1,3- are double
Double (4- amino-benzene oxygens) butane of (4- amino-benzene oxygens) propane, 1,4-, double (4- amino-benzene oxygens) pentanes of 1,5-, 1,3- are double
Double [2- (4- amino-benzene oxygens) ethyoxyl] ethane of (4- amino-benzene oxygens) -2,2- dimethylpropanes, 1,2-, double (the 4- ammonia of 9,9-
Base phenyl) fluorenes, 5 (6)-amino -1- (4- amino methyls) -1,3,3- trimethyl indanes, 1,4- double (4- amino-benzene oxygens) benzene, 1,
Double (3- amino-benzene oxygens) benzene of double (4- amino-benzene oxygens) benzene of 3-, 1,3-, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, 4,4 '-it is bis-
(3- amino-benzene oxygens) biphenyl, 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, double [4- (4- amino-benzene oxygens) phenyl]
Sulfone, double [4- (3- amino-benzene oxygens) phenyl] sulfones, 2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 3,3 '-dicarboxyls
Base -4,4 '-diaminodiphenyl-methane, 4,6- dihydroxy -1,3- phenylenediamines, 3,3 '-dihydroxy -4,4 '-diaminourea connection
Benzene, 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa, 3,3 ', 4,4 '-tetra-amino-biphenyl, 1,6- diamino hexanes, 1,3-
Double (3- aminopropyls) tetramethyl disiloxanes, 1- amino -3- amino methyl -3,5,5- trimethyl-cyclohexanes, 4,4 '-methylene
Double (4- cyclohexylamine), trans-1,4-cyclohexane diamines, two rings [2.2.1] heptane double (methyl amine), three rings [3.3.1.13.7] last of the ten Heavenly stems
Double [the 4- of alkane -1,3- diamines, 4- amino benzoic acid -4- aminobenzenes base ester, 2- (4- aminophenyls) amino benzoxazoles, 9,9-
(4- amino-benzene oxygens) phenyl] fluorenes, 2,2 '-bis- (3- sulfopropyls) -4,4 '-benzidines, 4,4 '-bis- (4- amino-benzene oxygens)
Biphenyl -3,3 '-disulfonic acid, 3,3 '-diamino diphenyl sulfone etc..Also, can also and with two or more in these materials.
In these diamines, 3,3 '-diamino diphenyl sulfone, two rings [2.2.1] heptane double (methyl amine), anti-is being used
In the case of the ester ring type diamines such as formula-Isosorbide-5-Nitrae-cyclohexane diamine, the transparency of obtained polyimides obtains more significantly changing
It is kind, also, using double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-, 2,2 '-bis- (trifluoromethyl) benzidine etc.
In the case of fluorinated diamine, the low dielectric for the polyimides that can more significantly improve to obtain, solvent solubility.These two
Amine relative to whole 1 mole of acid anhydrides (when the present invention the tetracarboxylic dianhydride and the other acid dianhydrides that are represented by above-mentioned formula (1) simultaneously
Also include other acid anhydrides in the case of), usually 0.9~1.1 mole, preferably used for the angle for improving the degree of polymerization
0.95~1.05 mole.
Also, common acid anhydrides when necessary, can be used together as copolymer composition.As the acid anhydrides that can be used together, can lift
Go out for example, pyromellitic dianhydride, the O-phthalic acid dianhydride of oxygen two, biphenyl -3,4,3 ', 4 '-tetracarboxylic dianhydride, Benzophenone -3,4,
3 ', 4 '-tetracarboxylic dianhydride, diphenyl sulfone -3,4,3 ', 4 '-tetracarboxylic dianhydride, 4,4 '-(2,2- hexafluoroisopropylidenyls) two adjacent benzene
Diformazan acid dianhydride, m- terphenyl -3,4,3 ', 4 '-tetracarboxylic dianhydride, p- terphenyls -3,4,3 ', 4 '-tetracarboxylic dianhydride, ring fourth
Alkane -1,2,3,4- tetracarboxylic dianhydrides, 1- carboxymethyl -2,3,5- pentamethylene tricarboxylic acids -2,6:3,5- dianhydrides, hexamethylene -1,2,4,
5- tetracarboxylic dianhydrides, butane -1,2,3,4- tetracarboxylic dianhydrides, 4- phenylene-ethynylenes phthalic anhydride, naphthalene -1,4,5,8- tetracarboxylic acids
Acid dianhydride, double (1,3- dioxo -1,3- dihydroisobenzofuran -5- carboxylic acids) Isosorbide-5-Nitrae-phenylene esters etc., these materials can also
And use two or more.In whole acid anhydrides in the case of other acid anhydrides, the dosage of other acid anhydrides is preferably 10 weights
More than % is measured, more preferably more than 30 weight %；On the other hand, preferably below 90 weight %, more preferably 70 weight % with
Under.By using other acid anhydrides more than 10 weight %, it can fully realize described later and be brought with other acid anhydrides
Raising physical property effect.On the other hand, can be abundant by the way that the dosage of other acid dianhydrides is controlled below 90 weight %
Realize the effect of the tetracarboxylic dianhydride containing ring-type hydrocarbon skeleton and ester group represented by above-mentioned formula (1) of the present invention.
As and with other acid anhydrides effect, for example, by and with 4,4 '-(2,2- hexafluoroisopropylidenyl), two adjacent benzene two
The fluorine-containing acid dianhydride such as formic acid dianhydride, the further low dielectric constant of the polyimides enabled to.It is also, firm and with have
In the case of the acid anhydrides such as the pyromellitic dianhydride of property skeleton, the obtained heat resistance of polyimides can be further improved.
The solvent that can be used when being manufactured as polyamic acid, as long as can dissolve as starting monomer, of the invention
The tetracarboxylic dianhydride represented by above-mentioned formula (1) and Diamines, and be inertia relative to the polyamic acid of these raw materials and generation,
Just there is no particular limitation for To.As such solvent, such as DMF, N, N- dimethylacetamides can be used
The chain ester series solvent such as the amide solvents such as amine, METHYLPYRROLIDONE, butyl acetate, ethyl acetate, isobutyl acetate, γ-
The carbonate solvents such as the ring-type ester solvent such as butyrolactone, γ-hexalactone, 6-caprolactone, ethylene carbonate, propene carbonate, three is sweet
Alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol methyl acetate, 2- methyl glycol acetates, ethyl cellosolve acetic acid
The binary alcohol series solvents such as ester, butyl cellosolve acetate, dimethoxy-ethane, diethoxyethane, diethylene glycol (DEG), phenol, orthoresol,
The ether series solvent such as phenol series solvent, tetrahydrofuran, butyl ether, ether such as metacresol, paracresol, 3- chlorophenols, 4- chlorophenols, methyl are different
The alcohol systems such as the ketone series solvent such as butyl ketone, DIBK, cyclohexanone, methyl ethyl ketone, acetone, acetophenone, butanol, ethanol are molten
The sulfone series solvents such as the fragrant family solvent such as agent, dimethylbenzene, toluene, chlorobenzene, dimethyl sulfoxide (DMSO), sulfolane.It is preferred that N, N- can be enumerated
The amide solvents such as dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl-pyrrolidons.These solvents can use a kind,
Or it can be used in mixed way when necessary with two or more.
As the dosage of solvent, the total concentration of the monomer component (tetracarboxylic dianhydride+diamines) in reaction system is usually 5~
40 weight %, preferably 10~25 weight % amount.By being polymerize with the monomer concentration scope, can obtain uniform and high
The polyamic acid solution of the degree of polymerization.If also, polymerize with the concentration less than above-mentioned monomer concentration scope, cannot be enough
The degree of polymerization of high polyamic acid, the polyimide film finally given may become fragile；If with higher than above-mentioned monomer concentration scope
Concentration polymerize, then may result in monomer can not fully dissolve, or reaction solution becomes heterogeneity and gelation occurs.
What is obtained in aforementioned manners has the solution of the polyamic acid of the repeat unit represented by above-mentioned formula (2), generally, in side described later
It is used directly in method in polyimides step.
＜ has the polyimides and its manufacture method ＞ of the repeat unit represented by above-mentioned formula (3)
Next, to the polyimides with the repeat unit represented by above-mentioned formula (3) (hereinafter also referred to as the present invention's
Polyimides) it is described in detail.So-called polyimides of the invention, refer to the repeat unit represented by following formula (3)
Polyimides.
[changing 10]
(wherein, in above formula, x, R1、R2, m, n and Z it is as defined above.)
The polyimides with the repeat unit represented by above-mentioned formula (3) of the present invention can be by making to be obtained by the above method
, polyamic acid that have the repeat unit represented by above-mentioned formula (2) occurs dehydration closed-loop reaction (imidization reaction) and makes
Make.As the method for imidization reaction, can enumerate for example, hot-imide method or chemical imidization method.
First, hot-imide method is described in detail.As hot-imide method, for example, the polymerization of polyamic acid is molten
Liquid is cast on a glass, in a vacuum or in the inert atmosphere such as nitrogen, or is heated in atmosphere.For example, it can dry
In case, generally it is dried at 50~190 DEG C, preferably 100~180 DEG C, thus obtains the film of polyamic acid.
Next, can by by the film of obtained polyamic acid on a glass typically 200~400 DEG C, preferably 250
Heated at~350 DEG C, cause imidization reaction, obtain polyimide film.Heating-up temperature is fully entered from making imidization reaction
For capable angle, preferably more than 200 DEG C；For the angle of the heat endurance of the polyimide film of generation, preferably 400
Below DEG C.
Imidization reaction carries out being preferable in vacuum or inert atmosphere, but as long as imidization reaction temperature is only
It is high, then to carry out there will not be problem in atmosphere.
Next, chemical imidization method is described in detail.First, to obtain in aforementioned manners it is of the invention have by
Identical solvent during with polymerizeing is added in the polyamic acid solution for the repeat unit that above-mentioned formula (2) represents, reaching and being easy to stirring
Appropriate solution viscosity, side stirring, side instills the dehydration that the acid anhydrides by organic acid and the tertiary amine as base catalyst form
Closed loop agent (chemical imidization agent), stirred 1~72 hour at a temperature of 0~100 DEG C, preferably 10~50 DEG C, thus, it is possible to
Complete chemical imidization.As the organic acid anhydride that can be used in this case, acetic anhydride, propionic andydride etc. can be enumerated.At this
In a little organic acid anhydrides, for the easiness for handling and separating, preferably acetic anhydride.In addition, as base catalyst, can make
With pyridine, triethylamine, quinoline etc..In these base catalysts, for the easiness for handling and separating, pyridine is preferred
's.Organic acid anhydride amount in chemical imidization agent 1~10 times of mole of the theoretical dehydrating amount of polyamic acid scope, more
Preferably 2~10 times of moles.Also, the amount of base catalyst relative to organic acid anhydride amount 0.1~5 times of mole model
Enclose, the scope of more preferably 1~5 times mole.
Alkali and unreacted chemical acid imide have been mixed into the reaction solution obtained by above-mentioned chemical imidization method
The accessory substances such as agent, organic acid (hereinafter referred to as impurity), therefore, these materials can be removed and polyimides is divided
From refined.Refine using known method.For example, as most easy method, following method can be applicable：Acyl is sub-
The reaction solution of amination is added dropwise in substantial amounts of poor solvent, after separating out polyimides, is reclaimed polyimide powder, is washed repeatedly
Until removing impurity, it is dried under reduced pressure, obtains polyimide powder.Now, as the solvent that can be used, as long as it can separate out
Polyimides, impurity is effectively removed, easily dry solvent, for example, the alcohols such as water or methanol, ethanol, isopropanol is
Suitable, these material mixings can also be used.The concentration of polyimide solution when separating out is instilled in poor solvent
If too high, the polyimides that separates out is block in grain, may in this block residual impurity, or in the polyamides that will be obtained
Imines powder is re-dissolved in the time length needed when in solvent.On the other hand, if the concentration of polyimide solution is excessively dilute,
Substantial amounts of poor solvent is needed, the result is that, it is necessary to handle substantial amounts of solvent slop, it is thus possible to environmental pressure or manufacture can be increased
Cost uprises.Therefore, the concentration of polyimide solution when instilling poor solvent is below 20 weight %, more preferably 10 weights
Measure below %.The amount of the poor solvent now used is preferably more than 1 times of weight 1.5~10 weights relative to polyimide solution
Amount times amount is suitable.Obtained polyimide powder is reclaimed, residual solvent is removed by vacuum drying or heated-air drying etc..
As for drying temperature and time, as long as the temperature that polyimides undergoes no deterioration, is not just limited, such as at 30~150 DEG C
Dry.
Polyimides is being made in the polyimide powder of the thus obtained repeat unit for having and being represented by above-mentioned formula (3)
In the case of film, it is necessary to the polyimide powder with the repeat unit represented by above-mentioned formula (3) is dissolved in solvent and formed
Polyimide solution.As the solvent that can be used, if using with use and processing conditions it is suitable, dissolving polyamides
The solvent of imines powder, specifically, it can use for example, DMF, DMA, N-
The amide solvents such as N-methyl-2-2-pyrrolidone N, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, α-
The carbon such as the ester solvents such as methyl-gamma-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate, ethylene carbonate, propene carbonate
The binary alcohol series solvent such as acid esters solvent, diethylene glycol dimethyl ether, triethylene glycol, triglyme, phenol, m- methylphenol,
The phenol series solvents such as p- methylphenol, ortho-methyl phenol, 3- chlorophenols, 4- chlorophenols, cyclopentanone, cyclohexanone, acetone, methyl second
The ketone series solvents such as base ketone, DIBK, methyl iso-butyl ketone (MIBK), tetrahydrofuran, Isosorbide-5-Nitrae-dioxanes, dimethoxy-ethane, diethyl
The ether series solvents such as epoxide ethane, butyl ether；In addition, acetophenone, DMI, ring fourth can also be used
Sulfone, dimethyl sulfoxide (DMSO), propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2- methyl glycol acetates, ethyl
Cellosolve acetate, butyl cellosolve acetate, butanol, ethanol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, Mineral spirits, naphtha
The general solvents etc. such as system, these solvents can use a kind, or can also two or more be used in mixed way.Polyimide powder it is molten
Solution method can be：In atmosphere or in inert atmosphere, dissolve, formed within the scope of the temperature below the boiling point of room temperature~solvent
Polyimide solution.
Can be by the way that thus obtained polyimide solution be for example cast on glass plate, in a vacuum or nitrogen etc. is lazy
In property atmosphere, or heated in atmosphere to obtain polyimide film.For example, can in an oven, generally 200~
Dried at 400 DEG C, preferably 250~350 DEG C, thus obtain polyimide film.The manufacture of polyimide film is in a vacuum or inertia
It is preferable to be carried out in atmosphere, but as long as temperature is not too high, carries out there will not be problem in atmosphere.
On by the above method obtain have by above-mentioned formula (3) represent repeat unit polyimides molecular weight,
The molecular weight obtained by assay method described later is preferably more than 10,000 with Weight-average molecular gauge, and more preferably more than 20,000, enter
One step preferably more than 40,000, also, less than 600,000 be preferable, less than 500,000 be it is furthermore preferred that less than 300,000 be further preferred
's.When the molecular weight of polyimides is more than 10,000, can be molded, and be easy to keep good mechanical characteristic.Also, work as
When the molecular weight of polyimides is less than 300,000, in most cases, easily controllable molecular weight during synthesis, and readily available viscosity
Appropriate solution, processing are easy.Also, the viscosity of polyimide solution can reflect the molecular weight of polyimides.
The dielectric of the polyimides with the repeat unit represented by above-mentioned formula (3) of the invention obtained by the above method
Rate is generally below 3.0, and preferably less than 2.9, interlayer dielectric use can be suitable as.Also, polyimide film
400nm light transmittances (T400) also there is high level, therefore the transparency is excellent；Further, for tetrahydrofuran, cyclopentanone, N, N- bis-
NMF, DMA, METHYLPYRROLIDONE, the dissolubility of gamma-butyrolacton equal solvent are also excellent,
Therefore low dielectric transparency polyimides is used as, optical material can be suitable as, electronic material uses.
【Embodiment】
Embodiments of the invention are following present, but the scope of the present invention is not limited to these embodiments.
(1) NMR is determined
Using tetramethylsilane as internal standard compound, the use of weight DMSO is solvent, is recorded with JEOL-ESC400 spectrometers1H-
NMR、13C-NMR。
(2) LC-MS is determined
LC-MS is separated with following condition determination, is carried out mass spectral analysis, identifies purpose thing.
Device：(strain) Waters systems " XevoG2Q-Tof "
Post：L-Column2ODS
(2 μm, 2.1mm φ × 100mm)
Column temperature：40℃
Detection wavelength：UV220-500nm
Mobile phase：The formic acid water of A liquid=0.1%, B liquid=methanol
Mobile phase flow rate：0.3mL/ minutes
Mobile phase gradient：B liquid concentration：80% (0 minute) → 80% (after 10 minutes) → 100% (after 15 minutes)
Detection method：Q-Tof
Ionization method：APCI (-) method
Ion gun：150 DEG C of temperature
Sampling spiroid：Voltage 60V, air-flow 50L/h
Desolventizing gas：500 DEG C of temperature, air-flow 1000L/h
(3) HPLC purity
Purity using the value of area percentage when carrying out HPLC measure by the use of following condition determinations as each compound.
Liquid chromatogram measuring condition：
Device：Society of Hitachi L-2130
Post：ZORBAXCN (5 μm, 4.5mm φ × 250mm)
Mobile phase：Hexane/THF, flow：1.0ml/min
Column temperature：40 DEG C, Detection wavelength：UV254nm
(4) weight average molecular weight of polyamic acid
Weight average molecular weight is determined with following condition determination.(polystyrene conversion)
Device：Eastern Cao's (strain) HLC-8320GPC processed
Post：TSK-GELSuperAWM-H(6.0mmI.D.×15cm)
Mobile phase：DMF, flow：1.0ml/min
Column temperature：40℃
(5) measure of fusing point
Using differential scanning calorimeter (SII TECHNOLOGY (strain) EXSTARDSC220 processed), with 10 DEG C/min of liter
Warm velocity determination.
(6) measure of glass transition temperature (Tg)
Using differential scanning calorimeter (SII TECHNOLOGY (strain) EXSTARDSC220 processed), with 20 DEG C/min of liter
Warm velocity determination.
(7) 5% weight reduce temperature (Td 5) measure
Using apparatus for thermal analysis ((strain) RIGAKU ThermoPlus EvoIITG-DTA8121/S), with 10 DEG C/min's
Determination of heating rate.
(8) measure of cutoff wavelength
Using spectrophotometer ((strain) Shimadzu Seisakusho Ltd. UV-2450), the 200~800nm for determining polyimide film is saturating
Light rate.Light transmittance is reached into less than 0.5% wavelength as cutoff wavelength.Cutoff wavelength is shorter, the transparency of polyimide film
Better.
(9) light transmittance (T400) measure
Using spectrophotometer ((strain) Shimadzu Seisakusho Ltd. UV-2450), the 400nm light transmittances of polyimide film are determined.
Light transmittance is higher, and the transparency of polyimide film is better.
(10) dielectric constant (ε)
Using abbe's refractometer ((strain) ATAGO multi-wavelengths abbe's refractometer DR-M2), determined on polyimide film flat
Line direction (nin) and vertical direction (nout) refractive index (wavelength：589nm), the mean refraction of polyimide film is obtained with following formula
Rate (nav)。
nav=(2nin+nout)/3
According to the mean refractive index (nav), the dielectric constant (ε) of the polyimide film under 1MHz is calculated according to following formula.
ε=1.1 × nav 2
(11) solvent solubility
Obtained polyimide film or powder 20mg are put into DMAC N,N' dimethyl acetamide (DMAc), N- methyl -2- pyrroles
In alkanone (NMP), tetrahydrofuran (THF), m- methylphenol (m-CR) 1mL, dissolubility is tested.With rank as described below come
Evaluate solvent solubility.
〇：Dissolve at room temperature.
△：Dissolve by heating, even if cooled to will not also be separated out after room temperature.
×：It is insoluble
1. the manufacture of the tetracarboxylic dianhydride containing ring-type hydrocarbon skeleton and ester group represented by above-mentioned formula (1)
The ＞ of ＜ embodiments 1
(among the tetracarboxylic anhydride that above-mentioned formula (1) represents, by tetracarboxylic dianhydride's (above-mentioned formula (1) of following formula (1-A) expression
In, m=n=1, x=5, R1And R2For methyl) Production Example)
[changing 11]
To equipped with thermometer, dropping funel, stirring rod 1L 4 mouthfuls of flasks in load Trimellitic Anhydride Chloride 83.0g
(394.2mmol), dimethoxy-ethane 100.0g, after stirring all dissolvings, begin to cool down.At 0 DEG C~9 DEG C, thereto
1,1- double (4- hydroxy-3-methyls phenyl) cyclododecane 50.0g (131.4mmol), dimethoxy second are instilled with the time of 1 hour
Alkane 150.0g and pyridine 31.2g (394.2mmol) mixed dissolution thing.Then, 0 DEG C~5 DEG C of temperature is kept, stirs 30 points
Clock.55 DEG C, after heating are then heated to, keeps 55 DEG C~60 DEG C of temperature, stirs 4 hours, then stirs 2 at 65~70 DEG C
Hour.Stop heating, be put into dimethoxy-ethane 228.8g, filtered at 25 DEG C~26 DEG C, 3 are washed with dimethoxy-ethane
It is secondary, obtain coarse crystallization.Acetonitrile is added into coarse crystallization and is heated to reflux the operation of 1 hour and is repeated 2 times, thus obtains white
Crystallize 57.08g (yield 59.6%, purity 99.2%).According to Fig. 11Shown in H-NMR spectrums, Fig. 213C-NMR is composed and figure
Mass spectral analysis figure shown in 3, it is thus identified that obtained product is the tetracarboxylic dianhydride represented by above-mentioned formula (1-A).Hereinafter, to obtaining
The tetracarboxylic dianhydride represented by above-mentioned formula (1-A)1H-NMR and13C-NMR is described in detail.
The obtained tetracarboxylic dianhydride's represented by above-mentioned formula (1-A)1H-NMR(DMSO-d6) spectrogram is as shown in Figure 1.
This, the peak in the range of 8.27~8.66ppm belongs to the benzene ring hydrogen of trimellitic acid, the peak in the range of 7.05~7.20ppm
Belong to the benzene ring hydrogen of double (4- hydroxy-3-methyls phenyl) the cyclododecane skeletons of 1,1-, 2.17ppm peak belongs on methyl
Hydrogen, the hydrogen that the peak in the range of 0.91~2.05ppm belongs on cyclododecane skeleton.In addition, the peak observed at 2.5ppm comes from
The water that the peak observed at solvent DMSO, 3.3ppm contains in DMSO.
13C-NMR(DMSO-d6) spectrum is as shown in Figure 2.Here, 162.3~162.5ppm and 128.7~136.9ppm model
The carbon that peak in enclosing belongs on trimellitic anhydride skeleton, 121.3ppm and 125.7~126.2ppm peak belong to the double (4- of 1,1-
Hydroxy-3-methyl phenyl) cyclododecane skeleton phenyl ring on carbon, the peak at 47.5ppm belongs to the carbon of methyl, 16.0~
32.4ppm peak belongs to the carbon of cyclododecane skeleton.In addition, the peak observed at 39.1~39.6ppm comes from solvent DMSO.
The mass spectrum numerical value and fusing point of the obtained tetracarboxylic dianhydride represented by above-mentioned formula (1-A) is as described below.
Mass spectrum numerical value (M-·)：728.26
Fusing point (DSC)：182℃
2. polyamic acid with the repeat unit represented by above-mentioned formula (2) and with the repetition represented by above-mentioned formula (3)
The manufacture of the polyimides of unit
The ＞ of ＜ embodiments 2
(among the polyamic acid that above-mentioned formula (2) represents, by the tetracarboxylic dianhydride represented by above-mentioned formula (1-A) and 4,4 '-
The polyamic acid that the reaction of oxygen diphenylamines (4,4 '-ODA) obtains (has the polyamide of the repeat unit represented by following formula (2-A)
Acid) manufacture)
[changing 12]
By the tetracarboxylic dianhydride 4.0g (5.49mmol) represented by above-mentioned formula (1-A) obtained by embodiment 1 with 4,4 '-
ODA1.1g (5.49mmol) is dissolved in DMA 45.9g at room temperature, and further reaction 27 is small at room temperature
When, synthesize by above-mentioned formula (2-A) represent polyamic acid DMA solution.The weight average molecular weight of polyamic acid
(Mw) it is 409,266.
The ＞ of ＜ embodiments 3
(among the polyimides represented by above-mentioned formula (3), by with the repeat unit represented by above-mentioned formula (2-A)
The manufacture of polyimides that the chemical imidization of polyamic acid obtains, that there is the repeat unit represented by following formula (3-A))
[changing 13]
To polyamide obtained with method same as Example 2, that there is the repeat unit represented by above-mentioned formula (2-A)
In DMA solution (the weight % of solute concentration 26.0) 73.5g of acid, DMA is added
73.5g, acetic anhydride 21.1g and pyridine 8.2g, it is stirred at room temperature 24 hours, thus synthesis has is represented by above-mentioned formula (3-A)
Repeat unit polyimides DMAC N,N' dimethyl acetamide solution (the weight % of solute concentration 13.0).
What is obtained has the DMAC N,N' dimethyl acetamide solution of the polyimides of the repeat unit represented by above-mentioned formula (3-A)
Further diluted with DMA, obtain 9 weight % solution, instilled in methanol 600g, separating out has by above-mentioned
The polyimides for the repeat unit that formula (3-A) represents.The polyimides of precipitation is filtered, dries, obtains light after being washed with methanol
The polyimide powder 17.8g of yellow.
METHYLPYRROLIDONE 22.8g is added into obtained polyimide powder 2.5g, is stirred until homogeneous, thus
Obtain the METHYLPYRROLIDONE solution of the polyimides with the repeat unit represented by above-mentioned formula (3-A).By the solution
After being applied on glass plate, heat 1 hour at 150 DEG C, heated 1 hour at 250 DEG C, obtain having by above-mentioned formula (3-
A) the film of the polyimides of the repeat unit represented.The thickness of film is about 20 μm.Obtained polyimides is given in table 1
The glass transition temperature (Tg) of film, 5% weight reduce temperature (Td 5), cutoff wavelength, 400nm light transmittances (T400), dielectric constant
The measurement result of (ε).Also, the dissolubility in various solvents is given in table 2.
The ＞ of ＜ embodiments 4
(among the polyamic acid that above-mentioned formula (2) represents, pass through the tetracarboxylic dianhydride and 9,9- represented by above-mentioned formula (1-A)
The polyamic acid that the reaction of double (4- aminophenyls) fluorenes (FDA) obtains (has the polyamides of the repeat unit represented by following formula (2-B)
Amino acid) manufacture)
[changing 14]
It will be obtained in embodiment 1 double with 9,9- by the tetracarboxylic dianhydride 7.0g (9.61mmol) that above-mentioned formula (1-A) represents
(4- aminophenyls) fluorenes 3.4g (9.61mmol) is dissolved in DMA 25.6g at room temperature, further in room
The lower reaction of temperature 24 hours, the N of polyamic acid of the synthesis with the repeat unit represented by above-mentioned formula (2-B), N- dimethylacetamides
Amine aqueous solution.The weight average molecular weight (Mw) of polyamic acid is 50,954.
The ＞ of ＜ embodiments 5
(among the polyimides represented by above-mentioned formula (3), by with the repeat unit represented by above-mentioned formula (2-B)
The manufacture of polyimides that the chemical imidization of polyamic acid obtains, that there is the repeat unit represented by following formula (3-B))
[changing 15]
What is obtained into embodiment 4 has the N of the polyamic acid of the repeat unit represented by above-mentioned formula (2-B), N- diformazans
In yl acetamide solution (the weight % of solute concentration 28.8) 34.8g, DMA 43.0g, acetic anhydride 9.5g are added
With pyridine 3.7g, it is stirred at room temperature 24 hours, obtains the polyimides with the repeat unit represented by above-mentioned formula (3-B)
DMAC N,N' dimethyl acetamide solution (the weight % of solute concentration 13.0).
What is obtained has the DMAC N,N' dimethyl acetamide solution of the polyimides of the repeat unit represented by above-mentioned formula (3-B)
Diluted with DMA, obtain 10 weight % solution, further diluted with METHYLPYRROLIDONE, obtain 9
Weight % solution, afterwards, instill in methanol 350g, it is sub- to separate out the polyamides with the repeat unit represented by above-mentioned formula (3-B)
Amine.The polyimides of precipitation is filtered, is dried after being washed with methanol, obtains flaxen polyimide powder 8.6g.
DMA 16.0g is added into obtained polyimide powder 4.0g, is stirred until homogeneous, is had
There is the DMAC N,N' dimethyl acetamide solution of the polyimides of the repeat unit represented by above-mentioned formula (3-B).By the solution in glass
After being coated with plate, heat 1 hour at 150 DEG C, heated 1 hour at 250 DEG C, obtain with by above-mentioned formula (3-B) expression
The film of the polyimides of repeat unit.The thickness of film is about 24 μm.The obtained glass of Kapton is given in table 1
Glass transition temperature (Tg), cutoff wavelength, 400nm light transmittances (T400), the measurement result of dielectric constant (ε).Also, table 2 gives
Dissolubility in various solvents.
The ＞ of ＜ embodiments 6
(among the polyamic acid represented by above-mentioned formula (2), by the tetracarboxylic dianhydride and 3 represented by above-mentioned formula (1-A),
The polyamic acid that the reaction of 3 '-diamino diphenyl sulfone (3,3 '-DDS) obtains (has the repeat unit represented by following formula (2-C)
Polyamic acid) manufacture)
[changing 16]
The tetracarboxylic dianhydride 4.0g (5.49mmol) and 3,3 '-two represented by above-mentioned formula (1-A) that will be obtained in embodiment 1
Aminodiphenyl base sulfone 1.4g (5.48mmol) is dissolved in DMA 13.3g at room temperature, further in room temperature
Lower reaction 24.5 hours, the N of polyamic acid of the synthesis with the repeat unit represented by above-mentioned formula (2-C), N- dimethylacetamides
Amine aqueous solution.The weight average molecular weight (Mw) of polyamic acid is 54,896.
The ＞ of ＜ embodiments 7
(among the polyimides represented by above-mentioned formula (3), by with the repeat unit represented by above-mentioned formula (2-C)
The manufacture of polyimides that the chemical imidization of polyamic acid obtains, that there is the repeat unit represented by following formula (3-C))
[changing 17]
What is obtained into embodiment 6 has the N of the polyamic acid of the repeat unit represented by above-mentioned formula (2-C), N- diformazans
In yl acetamide solution (the weight % of solute concentration 28.8) 18.6g, add DMA 8.2g, acetic anhydride 5.6g and
Pyridine 2.2g, it is stirred at room temperature 25 hours, thus obtains the polyimides with the repeat unit represented by above-mentioned formula (3-C)
DMAC N,N' dimethyl acetamide solution (the weight % of solute concentration 20.0).
The DMAC N,N' dimethyl acetamide of the obtained polyimides with the repeat unit represented by above-mentioned formula (3-C) is molten
Drop enters in methanol 200g, separates out the polyimides with the repeat unit represented by above-mentioned formula (3-C).The polyamides of precipitation is sub-
Amine filters, and is dried after being washed with methanol, obtains flaxen polyimide powder 5.0g.
DMA 16.0g is added into obtained polyimide powder 4.0g, is stirred until homogeneous, thus
To the DMAC N,N' dimethyl acetamide solution of the polyimides with the repeat unit represented by above-mentioned formula (3-C).It is molten by what is obtained
After liquid is coated with a glass, heat 1 hour at 150 DEG C, heated 1 hour at 250 DEG C, obtain having by above-mentioned formula (3-
C) the film of the polyimides of the repeat unit represented.The thickness of film is about 20 μm.Obtained polyimides is given in table 1
Glass transition temperature (Tg), cutoff wavelength, the 400nm light transmittances (T of film400), the measurement result of dielectric constant (ε).Also,
Table 2 gives the dissolubility in various solvents.
The ＞ of ＜ embodiments 8
(among the polyamic acid represented by above-mentioned formula (2), by the tetracarboxylic dianhydride and 2 represented by above-mentioned formula (1-A),
The reaction of 2 '-bis- (trifluoromethyls) -4,4 '-benzidines (alias 2,2 '-bis- (trifluoromethyl) benzidine) (TFMB) obtains
Polyamic acid (have by the polyamic acid of the repeat unit represented with following formula (2-D)) manufacture)
[changing 18]
The tetracarboxylic dianhydride 4.0g (5.49mmol) that the above-mentioned formula (1-A) obtained in embodiment 1 is represented with 2,2 '-it is bis-
(trifluoromethyl) -4,4 '-benzidine (alias 2,2 '-bis- (trifluoromethyl) benzidine) 1.76g (5.49mmol) is in room temperature
Under be dissolved in DMA 14.24g, further at room temperature react 24 hours, synthesis have by above-mentioned formula (2-
D) the DMAC N,N' dimethyl acetamide solution of the polyamic acid of the repeat unit represented.The weight average molecular weight (Mw) of polyamic acid is
136,263。
The ＞ of ＜ embodiments 9
(among the polyimides represented by above-mentioned formula (3), by with the repeat unit represented by above-mentioned formula (2-D)
The manufacture of polyimides that the chemical imidization of polyamic acid obtains, that there is the repeat unit represented by following formula (3-D))
[changing 19]
What is obtained into embodiment 8 has the N of the polyamic acid of the repeat unit represented by above-mentioned formula (2-D), N- diformazans
In yl acetamide solution (the weight % of solute concentration 28.8) 20.0g, DMA 8.81g, acetic anhydride 5.6g are added
With pyridine 2.2g, it is stirred at room temperature 24 hours, it is sub- thus obtains the polyamides with the repeat unit represented by above-mentioned formula (3-D)
The DMAC N,N' dimethyl acetamide solution (the weight % of solute concentration 20.0) of amine.
The DMAC N,N' dimethyl acetamide of the obtained polyimides with the repeat unit represented by above-mentioned formula (3-D) is molten
Drop enters in methanol 200g, separates out the polyimides with the repeat unit represented by above-mentioned formula (3-D).The polyamides of precipitation is sub-
Amine filters, and is dried after being washed with methanol, obtains the polyimide powder 5.6g of white.
DMA 20.0g is added into obtained polyimide powder 5.0g, is stirred until homogeneous, is had
There is the DMAC N,N' dimethyl acetamide solution of the polyimides of the repeat unit represented by above-mentioned formula (3-D).Obtained solution is existed
After being coated with glass plate, heat 1 hour at 150 DEG C, heated 1 hour at 250 DEG C, obtain having by above-mentioned formula (3-D) table
The film of the polyimides of the repeat unit shown.The thickness of film is about 28 μm.Obtained Kapton is given in table 1
Glass transition temperature (Tg), cutoff wavelength, 400nm light transmittances (T400), the measurement result of dielectric constant (ε).Also, table 2 is given
The dissolubility gone out in various solvents.
The ＞ of ＜ comparative examples 1
(pass through the acid dianhydride (following formula (8-A)) with fluorene skeleton and ester group
[changing 20]
It is that the reaction of 4 '-oxygen diphenylamines (4,4 '-ODA) obtains, there is the repeat unit that is represented by following formula (8-C) with 4
The Production Example of polyimides)
[changing 21]
According to the record of Japanese Laid-Open Patent Publication 2007-91701 publications, obtain having by above-mentioned formula (8-C) table
The film of the polyimides (polyimides with fluorene skeleton and ester group) of the repeat unit shown.In addition, in generation polyimides
The weight average molecular weight (Mw) of polyamic acid before is 150,356, and the thickness of obtained film is about 22 μm.Given in table 1
The glass transition temperature (Tg) of obtained Kapton, 5% weight reduce temperature (Td 5), cutoff wavelength, 400nm printing opacities
Rate (T400), the measurement result of dielectric constant (ε).Also, table 2 gives the dissolubility in various solvents.
[table 1]
[table 2]
Claims (3)
1. the tetracarboxylic dianhydride represented by following formula (1),
[changing 1]
Wherein, x represents 1~11 integer, R1And R2Alkyl, halogen atom, hydroxyl, the carbon number of carbon number 1~12 are represented independently of one another
4~16 cycloalkyl or the aromatic series base of carbon number 6~12；Multiple R be present1And/or R2In the case of, each group it is identical or
It is different；M and n represents 0 or 1~4 integer independently of one another.
2. the polyamic acid with the repeat unit represented by following formula (2),
[changing 2]
Wherein, x represents 1~11 integer, R1And R2Alkyl, halogen atom, hydroxyl, the carbon number of carbon number 1~12 are represented independently of one another
4~16 cycloalkyl or the aromatic series base of carbon number 6~12；Multiple R be present1And/or R2In the case of, each group it is identical or
It is different；M and n represents 0 or 1~4 integer independently of one another；Also, Z represents diamines residue.
3. the polyimides with the repeat unit represented by following formula (3),
[changing 3]
Wherein, x represents 1~11 integer, R1And R2Alkyl, halogen atom, hydroxyl, the carbon number of carbon number 1~12 are represented independently of one another
4~16 cycloalkyl or the aromatic series base of carbon number 6~12；Multiple R be present1And/or R2In the case of, each group it is identical or
It is different；M and n represents 0 or 1~4 integer independently of one another；Also, Z represents diamines residue.
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| JP2016-029454 | 2016-02-19 | ||
| PCT/JP2016/064613 WO2016190170A1 (en) | 2015-05-27 | 2016-05-17 | Tetracarboxylic acid dianhydride having cyclic hydrocarbon skeleton and ester group, polyamic acid and polyimide |
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| CN109369914A (en) * | 2018-09-26 | 2019-02-22 | 江阴骏驰复合材料有限公司 | A kind of high molecular material compositions and the preparation method and application thereof |
| CN111303424A (en) * | 2020-04-15 | 2020-06-19 | 江阴骏驰新材料科技有限公司 | Transparent high polymer material composition and application thereof |
| CN116096784A (en) * | 2021-04-09 | 2023-05-09 | 三菱瓦斯化学株式会社 | Bisimide phenol compounds |
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| JP7259575B2 (en) * | 2019-06-17 | 2023-04-18 | 荒川化学工業株式会社 | Polyimide, adhesive, film-like adhesive, adhesive layer, adhesive sheet, resin-coated copper foil, copper-clad laminate, printed wiring board, multilayer wiring board, and manufacturing method thereof |
| CN113896889B (en) * | 2020-07-06 | 2023-11-17 | 臻鼎科技股份有限公司 | Polyimide composition, polyimide film and polyimide copper-clad plate |
| CN117337314A (en) * | 2021-05-19 | 2024-01-02 | 三菱瓦斯化学株式会社 | Acid dianhydride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109369914A (en) * | 2018-09-26 | 2019-02-22 | 江阴骏驰复合材料有限公司 | A kind of high molecular material compositions and the preparation method and application thereof |
| CN109369914B (en) * | 2018-09-26 | 2020-08-07 | 江阴骏驰新材料科技有限公司 | High polymer material composition and preparation method and application thereof |
| CN111303424A (en) * | 2020-04-15 | 2020-06-19 | 江阴骏驰新材料科技有限公司 | Transparent high polymer material composition and application thereof |
| CN111303424B (en) * | 2020-04-15 | 2022-10-21 | 江阴骏驰新材料科技有限公司 | Transparent high polymer material composition and application thereof |
| CN116096784A (en) * | 2021-04-09 | 2023-05-09 | 三菱瓦斯化学株式会社 | Bisimide phenol compounds |
| CN116096784B (en) * | 2021-04-09 | 2023-08-15 | 三菱瓦斯化学株式会社 | Bisimide phenol compounds |
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| KR20180011764A (en) | 2018-02-02 |
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