CN109575282A - The manufacturing method of polyimides - Google Patents
The manufacturing method of polyimides Download PDFInfo
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- CN109575282A CN109575282A CN201810986098.0A CN201810986098A CN109575282A CN 109575282 A CN109575282 A CN 109575282A CN 201810986098 A CN201810986098 A CN 201810986098A CN 109575282 A CN109575282 A CN 109575282A
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of manufacturing method that the good polyimides of characteristic can be made steadily to polymerize when using two amine composition of dimer as raw material.The manufacturing method of polyimides uses following person: as two amine composition of dimer, (a) dimer diamines；(b) monoamine compound for the terminal carboxylic acid group of the unitary acid compound in the range of carbon number 10~40 being substituted by level-one amino methyl or amino and being obtained；(c) terminal carboxylic acid group of the polybasic acid compound with alkyl in the range of carbon number 41~80 is substituted by level-one amino methyl or amino and the amine compounds that obtain (wherein, except the dimer diamines) in, (a) content be 96 weight % or more, by GPC measure in tomographic map area percentage in terms of (b) and (c) add up to 4% or less.
Description
Technical field
The present invention relates to a kind of using dimer diamines as the manufacturing method of the polyimides of raw material.
Background technique
In recent years, along with the miniaturization of e-machine, lightweight, the development of space saving, to thin and light amount, with soft
Even if property, alternating bending also have excellent durability flexible printed wiring board (Flexible Printed Circuits,
FPC) need to increase.FPC in a limited space in can also three-dimensional and highdensity installation, therefore for example in hard disk drive
The electronic machines such as (Hard Disk Drive, HDD), Digital video disc (Digital Video Disk, DVD), smart phone
Its purposes is gradually expanded in the parts such as the wiring or cable of the moving part of device, connector.
In addition, the further development of the multifunction due to e-machine, it is also desirable to cope with the high frequency to transmitting signal.
When transmitting high-frequency signal, in the case that transmitting in transmission path loss is big, loss or the signal of electric signal can be generated
A problem that delay time is elongated.Therefore, the reduction for transmitting loss in FPC from now on also becomes important.It is required that reply high frequency
The FPC or solid of change.
And say, as being related to proposing using polyimides as the technology of the following layer of principal component by crosslinked polyimide tree
Rouge is applied in the adhesion agent layer of cover film, and the crosslinked polyimide resin is to make polyimides and at least two 1
Grade amino is reacted as the amine compounds of functional group and is obtained, and the polyimides is by dimeric dibasic acid (dimer fatty acid) etc.
Diamine compound derived from aliphatic diamine is raw material (for example, patent document 1).In addition, proposing the polyimides
It is applied in copper clad laminate with the resin combination of the thermosetting resins such as epoxy resin and crosslinking agent (for example, patent
Document 2).But in patent document 1 and patent document 2, the dimer diamines derived from the dimeric dibasic acid as contained in raw material
The influence of by-product in addition, does not account at all.
Known dimeric dibasic acid is in the feed using such as soya fatty acid, ready denier oil acid, rapeseed oil fatty acid
Natural acid and the oleic acid for refining these acid, linoleic acid, linolenic acid, sinapic acid etc. simultaneously carry out diels-Alder
The dimerized fatty acid for reacting (Diels-Alder reaction) and obtaining, the polybasic acid compound as derived from dimeric dibasic acid can
As the fatty acid more than fatty acid or trimerizing of raw material composition and obtain (for example, patent document 3).
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2013-1730 bulletin
[patent document 2] Japanese Patent Laid-Open 2017-119361 bulletin
[patent document 3] Japanese Patent Laid-Open 2017-137375 bulletin
Summary of the invention
[problem to be solved by the invention]
As control using polyimides as the method for the physical property of the resin of principal component, it is important that control is used as polyimides
Predecessor polyamic acid or polyimides molecular weight.However, in the case where application dimer diamines is as raw material, it can
Comprising using in the state of by-product other than the dimer diamines as derived from dimeric dibasic acid, therefore, it is difficult to by polyimides
Molecular weight controls in a certain range.
Therefore, the purpose of the present invention is to provide one kind to keep characteristic good when using dimer diamines as raw material
The manufacturing method that good polyimides steadily polymerize.
[technical means to solve problem]
The present inventor et al. has carried out making great efforts research, as a result using two amine composition of dimer as the polyimides of raw material
In manufacture, being conceived to the amine compounds other than dimer diamines influences the molecular weight bring of polyimides, and discovery passes through control
The amount of these amine compounds is made, can steadily manufacture polyimides, so as to complete the present invention.
That is, the present invention be a kind of polyimides manufacturing method, wherein the polyimides be make tetracarboxylic anhydride ingredient with
Diamine component containing two amine composition of dimer reacts, and two amine composition of dimer is by two of dimeric dibasic acid
It is principal component that terminal carboxylic acid group, which is substituted by dimer diamines made of level-one amino methyl or amino,.
In the manufacturing method of polyimides of the invention, wherein about two amine composition of dimer, following compositions
(a)~ingredient (c):
(a) dimer diamines；
(b) by the terminal carboxylic acid group of the unitary acid compound in the range of carbon number 10~40 be substituted by level-one amino methyl or
Amino and the monoamine compound obtained；
(c) terminal carboxylic acid group of the polybasic acid compound with alkyl in the range of carbon number 41~80 is substituted by level-one
Amino methyl or amino and in the amine compounds (wherein, except the dimer diamines) that obtain,
The content of (a) ingredient is 96 weight % or more relative to two amine composition of dimer,
With the area percentage of the tomographic map in the measurement using gel permeation chromatography of two amine composition of dimer
Ingredient (b) described in rate meter and ingredient (c) add up to 4% or less.
The manufacturing method of polyimides of the invention can also be 3% for the area percentage of the tomographic map of described (c) ingredient
Below.
The manufacturing method of polyimides of the invention can also be the ingredient (b) and the face of the tomographic map of ingredient (c)
The ratio (b/c) of product percentage is 1 or more, can also rubbing for the tetracarboxylic anhydride ingredient and the diamine component in the situation
You are 0.97 or more and less than by 1.0 than (tetracarboxylic anhydride ingredient/diamine component).
The manufacturing method of polyimides of the invention can also be the ingredient (b) and the face of the tomographic map of ingredient (c)
The ratio (b/c) less than 1 of percentage is accumulated, can also be the tetracarboxylic anhydride ingredient and mole of the diamine component in the situation
It is 0.97 or more and 1.1 or less than (tetracarboxylic anhydride ingredient/diamine component).
The manufacturing method of polyimides of the invention can also be 40,000 for the weight average molecular weight of the polyimides
In the range of~150,000.
[The effect of invention]
The amine other than dimer diamines in manufacturing method control two amine composition of dimer of polyimides of the invention
The content of compound, therefore using two amine composition of dimer to can inhibit the poly- of every batch of in the manufacture of the polyimides of raw material
The unevenness of imido weight average molecular weight.As a result, can steadily the good polyimides of manufacturing characteristics, it can be achieved that quality
Stabilisation and yield raising.
Specific embodiment
Detailed description of embodiments of the present invention.
The manufacturing method of polyimides of the invention be to make tetracarboxylic anhydride ingredient with containing two amine composition of dimer
Diamine component reaction and the polyamic acid of predecessor obtained carries out imidizate, two amine composition of dimer is with by two
It is principal component that two terminal carboxylic acid groups of polyacids, which are substituted by dimer diamines made of level-one amino methyl or amino,.
[tetracarboxylic anhydride ingredient]
Tetracarboxylic anhydride ingredient used in polyimides as embodiments of the present invention, such as can enumerate: 3,3', 4,
4'- biphenyltetracarboxylic dianhydride, pyromellitic acid anhydride, 1,4- phenylene bis- (trimellitic acid monoesters) dianhydrides, 3,3', 4,4'-
Diphenyl sulfone tetracarboxylic dianhydride, 4,4'- oxygroup diphthalic anhydrides, 2,3,3,4- biphenyltetracarboxylic dianhydride, 2,2,3,3- bis-
Benzophenonetetracarboxylic dianhydride, 2,3,3,4- benzophenone tetracarboxylic dianhydride or 3,3,4,4- benzophenone tetracarboxylic dianhydride, 2,3,
3,4- diphenyl ether tetracarboxylic dianhydride, bis- (2,3- dicarboxyphenyi) ether dianhydrides, 3,3,4,4- para-terpheny tetracarboxylic dianhydride, 2,3,
3,4- para-terpheny tetracarboxylic dianhydride or 2,2,3,3- para-terpheny tetracarboxylic dianhydride, bis- (2,3- the or 3,4- dicarboxyl benzene of 2,2-
Base) propane dianhydride, bis- (2,3- or 3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- or 3,4- dicarboxyphenyi) sulfone dianhydrides,
Bis- (2,3- or 3,4- dicarboxyphenyi) the ethane dianhydrides of 1,1-, 1,2,7,8- phenanthrene-tetracarboxylic dianhydride, 1,2,6,7- phenanthrene-tetrabasic carboxylic acid
Dianhydride or 1,2,9,10- phenanthrene-tetracarboxylic dianhydride, 2,3,6,7- anthracene tetracarboxylic dianhydride, bis- (3,4- dicarboxyphenyi) tetrafluoros of 2,2-
Propane dianhydride, 2,3,5,6- hexamethylene dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 2,3,6,
7- naphthalene tetracarboxylic acid dianhydride, 4,8- dimethyl -1,2,3,5,6,7- hexahydro naphthalene -1,2,5,6- tetracarboxylic dianhydride, dichloronaphtalene -1 2,6-,
4,5,8- tetracarboxylic dianhydride or 2,7- dichloronaphtalene -1,4,5,8- tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-) Tetrachloronaphthalene -1,
4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9-- tetracarboxylic dianhydride, 3,4,9,10-- tetracarboxylic dianhydride, 4,
5,10,11-- tetracarboxylic dianhydride or 5,6,11,12-- tetracarboxylic dianhydride, pentamethylene -1,2,3,4- tetracarboxylic dianhydride, pyrrole
Piperazine -2,3,5,8- tetracarboxylic dianhydride, pyrrolidines -2,3,4,5- tetracarboxylic dianhydride, thiophene -2,3,4,5- tetracarboxylic dianhydride, 4,4'-
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides of bis- (2,3- di carboxyl phenyloxy) diphenyl methane dianhydrides, 2,2-,
4,4'- (hexafluoroisopropyli,ene) diphthalic anhydrides, (trimellitic acid monoester anhydrides) bis- to benzene, the double trimellitic acids of ethylene glycol
The acid dianhydrides such as acid anhydride.Wherein, 2,2,3,3- benzophenone tetracarboxylic dianhydrides, 2,3,3,4- benzophenone tetrabasic carboxylic acids two especially are being used
Acid anhydride or 3, in the case where 3,4,4- benzophenone tetracarboxylic dianhydrides, ketone group present in molecular skeleton and aftermentioned ingredient sometimes
(b) or the amino of ingredient (c) reacts and forms C=N key, is easy to show effect of the invention.
[two amine composition of dimer]
Two amine composition of dimer used in the method for the present invention contains following compositions (a) and control composition (b) and ingredient
(c) amount.
(a) dimer diamines:
The dimer diamines of so-called (a) ingredient refers to that two terminal carboxylic acid groups (- COOH) of dimeric dibasic acid are substituted by level-one
Amino methyl (- CH2-NH2) or amino (- NH2) made of diamines.Dimeric dibasic acid is the intermolecular polymerization using unsaturated fatty acid
Reaction and the known binary acid obtained, industrialness manufacturing process in the industry cycle basic standardization, using clay catalyst etc.
Dimerization is carried out to the unsaturated fatty acid of carbon number 11~22 and is obtained.Industrial obtainable dimeric dibasic acid be by oleic acid or
The binary acid of carbon number 36 that the unsaturated fatty acids of the carbon numbers such as linoleic acid, linolenic acid 18 carries out dimerization and obtains is principal component,
According to the degree of purification, other polymerizations of monomer acids (carbon number 18), trimer acid (carbon number 54), carbon number 20~54 containing any amount
Fatty acid.In addition, remaining has double bond after dimerization, but in the present invention, and then carries out hydrogenation and make degree of unsaturation
Descender is also contained in dimeric dibasic acid.
Two amine composition of dimer, which can be used, passes through the refining methds such as molecular distillation for the dimer diamine contents of (a) ingredient
It improves to 96 weight % or more, preferably 97 weight % or more, the more preferably 98 above persons of weight %.By by (a) ingredient
Dimer diamine contents are set as 96 weight % or more, can inhibit the expansion of the molecular weight distribution of polyimides.Furthermore if technically
May, then the whole (100 weight %) of best two amine composition of dimer is made of the dimer diamines of (a) ingredient.
(b) by the terminal carboxylic acid group of the unitary acid compound in the range of carbon number 10~40 be substituted by level-one amino methyl or
Amino and the monoamine compound obtained:
Unitary acid compound in the range of carbon number 10~40 is derived from the range of the carbon number 10~20 of the raw material of dimeric dibasic acid
Interior unary unsaturated fatty acid and as dimeric dibasic acid manufacture when by-product carbon number 21~40 in the range of unitary
The mixture of acid compound.Monoamine compound is that the terminal carboxylic acid group of these unitary acid compounds is substituted by level-one amino methyl
Or amino and winner.
(b) monoamine compound of ingredient is the increased ingredient of molecular weight for inhibiting polyimides.In polyamic acid or polyamides
When the polymerization of imines, the amino of the simple function of the monoamine compound passes through the end anhydride group with polyamic acid or polyimides
Reaction, end anhydride group are sealed, and the molecular weight of polyamic acid or polyimides is inhibited to increase.
(c) terminal carboxylic acid group of the polybasic acid compound with alkyl in the range of carbon number 41~80 is substituted by level-one
Amino methyl or amino and the amine compounds (wherein, except the dimer diamines) obtained:
The polybasic acid compound with alkyl in the range of carbon number 41~80 is using pair when manufacture as dimeric dibasic acid
Tribasic acid compound in the range of the carbon number 41~80 of product is the polybasic acid compound of principal component.In addition, also may include carbon
Polymerized fatty acid other than the dimeric dibasic acid of number 41~80.Amine compounds are to replace the terminal carboxylic acid group of these polybasic acid compounds
The winner for level-one amino methyl or amino.
(c) amine compounds of ingredient contribute to the increased ingredient of molecular weight of polyimides.To be originated from the three of trimer acid
Amine object is that the amino of the trifunctional of principal component or more reacts with the end anhydride group of polyamic acid or polyimides and keeps polyamides sub-
The molecular weight of amine sharply increases.In addition, as carbon number 41~80 dimeric dibasic acid other than polymerized fatty acid derived from amine compounds
Also the reason of making the molecular weight of polyimides increase and become the gelation of polyamic acid or polyimides.
Two amine composition of dimer is by using gel permeation chromatography (Gel Permeation
Chromatography, GPC) measurement carry out each ingredient and quantify, but each ingredient in order to make dimer two amine composition
The confirmation of wave crest starting point, wave crest vertex and wave crest terminal is easy, and is used and combined using acetic anhydride and pyridine to dimer diamines
The sample that object is handled, in addition uses cyclohexanone as internal standard material.Using the sample prepared in this way, with
The area percentage of the tomographic map of GPC quantifies each ingredient.The wave crest starting point and wave crest terminal of each ingredient are set as each wave crest
The minimum value of curve carries out the calculating of the area percentage of tomographic map as benchmark.
In addition, two amine composition of dimer can for by using GPC measure and obtain tomographic map area percentage in terms of at
Point (b) and ingredient (c) add up to 4% or more, preferably less than 4%.By the way that ingredient (b) and the total of ingredient (c) are set as
4% hereinafter, can inhibit the expansion of the molecular weight distribution of polyimides.
In addition, (b) area percentage of the tomographic map of ingredient can for preferably 3% hereinafter, more preferably 2% hereinafter, into
And preferably 1% or less.By being set as in the range, the decline of the molecular weight of polyimides can inhibit, and then four can be expanded
The range of the molar ratio of the loading of carboxylic acid anhydride component and diamine component.Furthermore (b) ingredient can be free of combines in dimer diamines
In object.
In addition, (c) area percentage of the tomographic map of ingredient can for preferably 3% hereinafter, more preferably 2% hereinafter, into
And preferably 1% or less.By being set as in the range, sharply increasing for the molecular weight of polyimides can inhibit, and then can expand
The range of the molar ratio of the loading of big tetracarboxylic anhydride ingredient and diamine component.Furthermore (c) ingredient can be free of in dimer diamines
In composition.
In addition, the situation for being 1 or more in the ratio (b/c) of ingredient (b) and the area percentage of the tomographic map of ingredient (c)
Under, the molar ratio (tetracarboxylic anhydride ingredient/diamine component) of tetracarboxylic anhydride ingredient and diamine component can for preferably 0.97 or more and
Less than 1.0, by being set as the molar ratio, the control of the molecular weight of polyimides is become easier to.
In addition, the ratio (b/c) less than 1 of ingredient (b) and the area percentage of the tomographic map of ingredient (c) the case where
Under, the molar ratio (tetracarboxylic anhydride ingredient/diamine component) of tetracarboxylic anhydride ingredient and diamine component can for preferably 0.97 or more and
1.1 hereinafter, by being set as the molar ratio, the control of the molecular weight of polyimides is become easier to.
In the range of the weight average molecular weight of polyimides preferably such as 10,000~200,000, if the model
In enclosing, then the control of the weight average molecular weight of polyimides becomes easy.In addition, in the solid as such as FPC and
In the case where, the weight average molecular weight of polyimides is more preferably in the range of 40,000~150,000.In polyamides Asia
In the case where the weight average molecular weight of amine less than 40,000, there are the tendencies that resistance to mobility is deteriorated.On the other hand, if polyamides is sub-
The weight average molecular weight of amine is more than 150,000, then increases with there is excess stickiness and do not dissolve in solvent, when applying operation
It is easy to produce the undesirable tendency of uneven thickness, striped of following layer etc..
Two amine composition of dimer used in the present invention is preferably the purpose to reduce the ingredient other than dimer diamines
It is refined.As refining methd, there is no particular restriction, but preferably method well known to the way of distillation or precipitating purification etc..Purification
Preceding two amine composition of dimer can obtain commercially available product, such as can enumerate big (Croda Japan KK.) the company manufacture of Japanese standing grain
Puli's nurse (PRIAMINE) 1073 (trade name), Puli's nurse (PRIAMINE) 1074 (trade name) of the said firm, the said firm
Puli's nurse (PRIAMINE) 1075 (trade name) etc..
As the diamine compound other than dimer diamines used in polyimides, aromatic diamine chemical combination can be enumerated
Object, aliphatic diamine compound.It as these concrete example, can enumerate: Isosorbide-5-Nitrae-diaminobenzene (p-PDA；P-phenylenediamine), 2,
2'- dimethyl -4,4'- benzidine (m-TB), 2,2'- n-propyl -4,4'- benzidine (m-NPB), 4- aminobenzene
Base -4'- Aminobenzoate (APAB), 2,2- be bis--[4- (3- amino-benzene oxygen) phenyl] propane, bis- [4- (3- aminobenzene oxygen
Base) phenyl] sulfone, bis- [4- (3- amino-benzene oxygen)] biphenyl, bis- [1- (3- amino-benzene oxygen)] biphenyl, bis- [4- (3- aminobenzene oxygen
Base) phenyl] methane, bis- [4- (3- amino-benzene oxygen) phenyl] ethers, bis- [4- (3- amino-benzene oxygen)] benzophenone, 9,9- be bis-
[4- (3- amino-benzene oxygen) phenyl] fluorenes, 2,2- be bis--and [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2- be bis--[4- (3-
Amino-benzene oxygen) phenyl] hexafluoropropane, 3,3'- dimethyl -4,4'- benzidine, two-ortho-aminotoluene of 4,4'- methylene,
Two -2,6- xylidine of 4,4'- methylene, 4,4'- methylene -2,6- diethylaniline, 3,3'- diamino-diphenyl second
[1,4- phenylene is double by alkane, 3,3- benzidine, 3,3'- dimethoxy benzidine, 3,3'- diamino-para-terpheny, 4,4-
(1- methyl ethylidene)] dianil, 4,4- [1,3- phenylene is bis- (1- methyl ethylidene)] dianil, bis- (to aminocyclohexyls)
Methane, bis- (p- beta-amino-tert-butyl-phenyl) ethers, bis- (p- Beta-methyl-δ-Aminopentyl) benzene, the bis- (2- methyl -4- amino penta of p-
Base) benzene, bis- (1,1- dimethyl -5- Aminopentyl) benzene of p-, 1,5- diaminonaphthalene, 2,6- diaminonaphthalene, the bis- (beta-aminos-of 2,4-
Tert-butyl) toluene, 2,4 di amino toluene, meta-xylene -2,5- diamines, paraxylene -2,5- diamines, m-xylene diamine,
Paraxylene diamines, 2,6- diamino-pyridine, 2,5- diamino-pyridine, 2,5- diaminostilbene, 3,4- oxadiazoles, piperazine, 2- first
Oxygroup -4,4- diaminobenzene anilid, 4,4- diaminobenzene anilid, 1,3- bis- [2- (4- aminophenyl) -2- propyl]
The diamine compounds such as benzene, 6- amino -2- (4- amino-benzene oxygen) benzoxazoles, bis- (3- amino-benzene oxygen) benzene of 1,3-.
Polyimides can generate polyamic acid by reacting the tetracarboxylic dianhydride in solvent with diamine compound
After carry out heating closed loop and manufacture.For example, organic by being dissolved in tetracarboxylic dianhydride and diamine compound with substantially equimolar
In solvent, in the range of 0 DEG C~100 DEG C at a temperature of stir 30 minutes~24 hours and carry out polymerization reaction, can get and make
For the polyamic acid of the predecessor of polyimides.Reaction when, with the predecessor of generation in organic solvent become 5 weight %~
Mode in the range of 50 weight %, in the range of preferably 10 weight of weight %~40 % dissolves reacted constituent.As polymerization
Organic solvent used in reaction, such as can enumerate: n,N-Dimethylformamide (N, N-Dimethyl Formamide, DMF),
N, N- diethyl acetamide (N, N-dimethyl acetamide, DMAc), N, N- diethyl acetamide, N- methyl -2- pyrroles
Alkanone (N-Methyl-2-pyrrolidinone, NMP), 2- butanone, dimethyl sulfoxide (dimethyl sulfoxide,
DMSO), hexamethyl phosphoramide, N- methyl caprolactam, dimethyl suflfate, cyclohexanone, dioxanes, tetrahydrofuran, diethylene glycol (DEG) two
Methyl ether, triglyme, cresols etc..Can also by these solvents and with using two or more, and then can also and with dimethylbenzene, first
The aromatic hydrocarbon of benzene etc.In addition, the usage amount as the organic solvent, there is no particular restriction, is preferably adjusted to utilize
Polymerization reaction and the concentration of polyamic acid solution obtained becomes the usage amount of 5 weight of weight %~50 % or so and uses.
Synthesized polyamic acid is frequently advantageous that as action solvent solution, but can be optionally concentrated, be diluted
Or it is replaced into other organic solvents.In addition, the usual solvent solubility of polyamic acid is excellent, therefore it is advantageously used.Polyamide
In the range of the viscosity of acid solution is preferably 500cps~100,000cps.If being detached from the range, coating machine etc. is being utilized
Film is easy to produce the bad of uneven thickness, striped etc. when the coating operation of progress.
Make polyamic acid imidizate and form the method for polyimides there is no particular restriction, for example, can preferably using
The heat treatment heated in 1 hour~24 hours is spent under the conditions of temperature in the solvent in the range of 80 DEG C~400 DEG C.
In addition, can be heated in a certain temperature conditions about temperature, temperature can also be changed in the midway of step.
[embodiment]
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not exposed to any of these embodiments
It limits.Furthermore below in an example, as long as no special instructions, then various measurements, evaluation are based on following persons.
[measuring method of amine value]
Two amine composition of dimer that about 2g is weighed in the conical flask of 200mL~250mL uses phenolphthalein as instruction
Agent is added dropwise the alcohol repellency potassium hydroxide solution of 0.1mol/L until lightpink is presented in solution, and is dissolved in and is neutralized
Butanol about 100mL in.The phenolphthalein solution of~7 drop of 3 drop is added thereto, utilizes the alcohol repellency potassium hydroxide of 0.1mol/L on one side
Solution be stirred be added dropwise on one side sample solution become lightpink until.5 drop bromophenol blue solution are added thereto, it is sharp on one side
It is stirred and is added dropwise to until sample solution becomes yellow on one side with hydrochloric acid/aqueous isopropanol of 0.2mol/L.
Amine value is calculated using following formula (1).
Amine value={ (V2×C2)-(V1×C1)}×MKOH/m···(1)
Herein, amine value is value represented by mg-KOH/g, MKOHFor the molecular weight 56.1 of potassium hydroxide.In addition, V, C distinguish
For the volume and concentration of solution used in dropwise addition, subscript 1,2 respectively indicates the alcohol repellency potassium hydroxide solution of 0.1M, 0.2mol/L
Hydrochloric acid/aqueous isopropanol.In turn, m be gram represented by example weight.
[measurement of the weight average molecular weight (Mw) of polyimides]
Weight average molecular weight utilizes gel permeation chromatography (HLC-8220GPC manufactured using Tosoh limited liability company)
It is measured.Use polystyrene as standard substance, solvent is unfolded and uses tetrahydrofuran.
[calculating of the area percentage of GPC and tomographic map]
GPC is will to be combined using the THF of the acetic anhydride of 200 μ L, the pyridine of 200 μ L and 2mL to the dimer diamines of 20mg
Object has been carried out the solution of the 100mg of pre-treatment and has been diluted with the THF (cyclohexanone containing 1000ppm) of 10mL, and prepares sample
Product.The trade name manufactured using Tosoh limited liability company: HLC-8220GPC, in tubing string: TSK-gel G2000HXL,
G1000HXL, amount of flow: 1mL/min, tubing string (baking oven) temperature: 40 DEG C, injection rate: to prepared sample under conditions of 50 μ L
It is measured.Furthermore it for the amendment of delivery time, is handled cyclohexanone as standard substance.
At this point, in such a way that the wave crest vertex of the main wave crest of cyclohexanone became 31 minutes from the residence time 27 minutes and with certainly
The wave crest starting point of the main wave crest of the cyclohexanone starts until wave crest terminal to be adjusted as 2 minutes modes, and
In a manner of the wave crest vertex of main wave crest other than the wave crest in addition to cyclohexanone became 19 minutes from 18 minutes and from addition to institute
The wave crest starting point for stating the main wave crest other than the wave crest of cyclohexanone starts until wave crest terminal to become from 2 minutes 30 seconds 4 minutes
Under the conditions of, detect each ingredient (a)~ingredient (c):
(a) ingredient represented by main wave crest；
(b) it is detected on the basis of the minimum value of the time side in evening residence time in main wave crest and with the time later
Ingredient represented by GPC wave crest；
(c) it is detected on the basis of the minimum value of the time side of morning residence time in main wave crest and with the time earlier
Ingredient represented by GPC wave crest.
Contracted notation used in the present embodiment indicates compound below.Furthermore " % " of b ingredient, c ingredient refers to that GPC is surveyed
The area percentage of tomographic map in fixed.
BTDA:3,3', 4,4'- benzophenone tetracarboxylic dianhydride
DDA1: to the trade name of big (Croda Japan KK.) the limited liability company manufacture of Japanese standing grain: Puli's nurse
(PRIAMINE) 1075 carry out distillation refiner (a ingredient: 97 weight %, b ingredients: 0.4%, c ingredient: 2.1%, amine value:
206mgKOH/g)
DDA2: to the trade name of big (Croda Japan KK.) the limited liability company manufacture of Japanese standing grain: Puli's nurse
(PRIAMINE) 1074 carry out distillation refiner (a ingredient: 96 weight %, b ingredients: 0%, c ingredient: 3.6%, amine value:
210mgKOH/g)
DDA3: to the trade name of big (Croda Japan KK.) the limited liability company manufacture of Japanese standing grain: Puli's nurse
(PRIAMINE) 1074 carry out distillation refiner (a ingredient: 96 weight %, b ingredients: 0%, c ingredient: 3.9%, amine value:
210mgKOH/g)
DDA4: to the trade name of big (Croda Japan KK.) the limited liability company manufacture of Japanese standing grain: Puli's nurse
(PRIAMINE) 1074 carry out distillation refiner (a ingredient: 96 weight %, b ingredients: 0%, c ingredient: 3.7%, amine value:
208mgKOH/g)
DDA5: to the trade name of big (Croda Japan KK.) the limited liability company manufacture of Japanese standing grain: Puli's nurse
(PRIAMINE) 1075 carry out distillation refiner (a ingredient: 97 weight %, b ingredients: 2.8%, c ingredient: 1.0%, amine value:
210mgKOH/g)
NMP:N- N-methyl-2-2-pyrrolidone N
Bis- (3- amino-benzene oxygen) benzene of APB:1,3-
Bis- [4- (4- amino-benzene oxygen) phenyl] propane of BAPP:2,2-
Bis- (amino methyl) hexamethylenes of 1,3-BAC:1,3-
BisDA:4,4'- [propane -2,2- diyl is bis- (1,4- phenylene oxygen)] two O-phthalic acid dianhydrides (husky uncle basis
Innovate the manufacture of plastics (SABIC Innovative Plastics) contract company, trade name: BisDA-1000)
Furthermore the molecular weight of the DDA1~DDA5 is calculated using following formula (1).
Molecular weight=56.1 × 2 × 1000/ amine value (1)
[embodiment 1]
The BTDA (0.17203 mole) of 55.55g, the DDA1 of 94.45g are packed into the separate type flask of 1000ml
The dimethylbenzene of (0.17342 mole), the NMP of 210g and 140g is sufficiently mixed 1 hour at 40 DEG C, and it is molten to prepare polyamic acid
Liquid.The polyamic acid solution is warming up to 190 DEG C, heats 4 hours and is stirred, the dimethylbenzene of 140g is added, and is prepared
Complete (the solid component: 30 weight %, weight average molecular weight: 84,800) of polyimide solution 1 of imidizate.
[2~embodiment of embodiment 19]
Other than being set as the composition of raw material shown in table 1,2~polyamides of polyimide solution is prepared similarly to Example 1
Imide liquor 19.
[table 1]
The manufacture of polyimides in the range of being 40,000~150,000 by weight average molecular weight is illustrated in embodiment
1~embodiment 19.
In embodiment 1, embodiment 4, embodiment 6 and 7~embodiment of embodiment 9, acid anhydrides/diamines ratio is 0.992.Herein,
By the comparison of the weight average molecular weight of the polyimides in embodiment 1 and embodiment 7, b ingredient is shown to inhibit polyamides
The increased ingredient or c ingredient of the weight average molecular weight of imines are the weight average molecular weight for facilitating polyimides
Increased ingredient, showing c ingredient by the comparison of embodiment 4 and embodiment 6 is the weight average point for facilitating polyimides
Son measures increased ingredient.
According to the result of 7~embodiment of embodiment 9, it is thus identified that between the batch in the weight average molecular weight of polyimides
It is uneven small.In addition, according to the result of embodiment 2, embodiment 3 and embodiment 5, it is thus identified that by the way that acid anhydrides/dianhydride ratio to be set as
1.008, the weight average molecular weight of polyimides can be suppressed in the range of 44,790~48,450.In addition, according to implementation
The result of example 7, embodiment 10 and embodiment 11, it is thus identified that by making acid anhydrides/diamines ratio when b ingredient/c ingredient is 1 or more certainly
0.992 is reduced to 0.980, and it is 108,880 that the weight average molecular weight of polyimides can be made, which to increase from 67,820,.On the other hand,
According to the result of embodiment 1, embodiment 2 and embodiment 12, it is thus identified that by b ingredient/c ingredient it is less than 1 when make acid anhydrides/diamines
It is 1.020 than increasing from 0.992, the weight average molecular weight of polyimides can be made to be reduced to 40,520 from 84,800.
In 13~embodiment of embodiment 19, show use diamines other than two amine composition of dimer as diamines at
Point.According to the result of 13~embodiment of embodiment 15, it is thus identified that along with the reduction of the molar ratio of APB, the combination of dimer diamines
The ratio of c ingredient in object increases, and the weight average molecular weight of polyimides also increases.In addition, according to embodiment 13 and implementing
The result of example 18, it is thus identified that, can be by the weight averaged molecular of polyimides by making acid anhydrides/diamines ratio become 1.008 from 0.992
Amount control is 43,300.According to embodiment 16 and the result of embodiment 17, it is thus identified that even if change two amine composition of dimer with
Outer diamine component can also similarly control the weight average molecular weight of polyimides.In addition, according to embodiment 14 and embodiment
19 result, it is thus identified that even if change acid anhydrides/diamines ratio, can also similarly control the weight average molecular weight of polyimides.
More than, with the purpose of illustration, detailed description of embodiments of the present invention, but the present invention is not by the reality
Apply the restriction of mode.
Claims (5)
1. a kind of manufacturing method of polyimides, wherein the polyimides is to make tetracarboxylic anhydride ingredient and contain dimer diamines
The diamine component of composition reacts, and two amine composition of dimer is to replace the two of dimeric dibasic acid terminal carboxylic acid group
It is principal component for dimer diamines made of level-one amino methyl or amino, and the feature of the manufacturing method of the polyimides exists
In,
About two amine composition of dimer, following compositions (a)~ingredient (c):
(a) dimer diamines；
(b) terminal carboxylic acid group of the unitary acid compound in the range of carbon number 10~40 is substituted by level-one amino methyl or amino
And the monoamine compound obtained；
(c) terminal carboxylic acid group of the polybasic acid compound with alkyl in the range of carbon number 41~80 is substituted by level-one amino
Methyl or amino and in the amine compounds that obtain,
The ingredient (c) does not include the dimer diamines,
The content of the ingredient (a) is 96 weight % or more relative to two amine composition of dimer,
In terms of the area percentage of the tomographic map in the measurement using gel permeation chromatography of two amine composition of dimer
The ingredient (b) and ingredient (c) add up to 4% or less.
2. the manufacturing method of polyimides according to claim 1, which is characterized in that the tomographic map of the ingredient (c)
Area percentage is 3% or less.
3. the manufacturing method of polyimides according to claim 1 or 2, which is characterized in that the ingredient (b) and ingredient
(c) ratio (b/c) of the area percentage of the tomographic map is 1 or more, the tetracarboxylic anhydride ingredient and the diamine component
Molar ratio (tetracarboxylic anhydride ingredient/diamine component) be 0.97 or more and less than 1.0.
4. the manufacturing method of polyimides according to claim 1 or 2, which is characterized in that the ingredient (b) and ingredient
(c) ratio (b/c) less than 1 of the area percentage of the tomographic map, the tetracarboxylic anhydride ingredient and the diamine component
Molar ratio (tetracarboxylic anhydride ingredient/diamine component) is 0.97 or more and 1.1 or less.
5. the manufacturing method of polyimides according to claim 1 or 2, which is characterized in that the weight of the polyimides
In the range of average molecular weight is 40,000~150,000.
Applications Claiming Priority (2)
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| JP2017191995A JP7486279B2 (en) | 2017-09-29 | 2017-09-29 | Polyimide manufacturing method |
| JP2017-191995 | 2017-09-29 |
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| JP (3) | JP7486279B2 (en) |
| KR (1) | KR102610515B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003469A (en) * | 2017-12-28 | 2019-07-12 | 日铁化学材料株式会社 | Two amine composition of dimer, its manufacturing method and resin film |
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| CN112778522A (en) * | 2019-11-07 | 2021-05-11 | 住友化学株式会社 | Polyamide-imide resin, optical film, and flexible display device |
| JP2023083146A (en) * | 2021-12-03 | 2023-06-15 | 住友化学株式会社 | Method for producing polyimide-based resin |
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| JP2024003240A (en) | 2024-01-11 |
| JP2019065181A (en) | 2019-04-25 |
| KR102610515B1 (en) | 2023-12-07 |
| JP7486279B2 (en) | 2024-05-17 |
| JP2022066412A (en) | 2022-04-28 |
| KR20190038361A (en) | 2019-04-08 |
| TW201918504A (en) | 2019-05-16 |
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