CN105829400A

CN105829400A - Method for producing polyimide, and polyimide obtained using such production method

Info

Publication number: CN105829400A
Application number: CN201480066676.9A
Authority: CN
Inventors: 松本利彦; 小松伸; 小松伸一
Original assignee: Tokyo Polytechnic University; JX Nippon Oil and Energy Corp
Current assignee: Tokyo Polytechnic University; Eneos Corp
Priority date: 2013-12-05
Filing date: 2014-11-28
Publication date: 2016-08-03
Also published as: TW201533096A; JP2015108092A; WO2015083649A1; KR20160096123A

Abstract

The invention relates to a method for producing polyimide, and a polyimide obtained using such a production method. Provided is a method for producing a polyimide, which obtains a polyimide having a repeating unit represented by general formula (2) [in the formula, R1 and R2 are synonymous with R1 and R2 in general formula (1)] by imidizing a poly(amic acid) having a repeating unit represented by general formula (1) [in the formula, R1 denotes a specific group, and R2 denotes a specific group] by using a mixture that contains this poly(amic acid), a halogen-based carboxylic acid anhydride and an aliphatic tertiary amine.

Description

The manufacture method of polyimides and by the polyimides obtained by this manufacture method

Technical field

The present invention relates to the manufacture method of a kind of polyimides and by the polyimides obtained by this manufacture method.

Background technology

In recent years, carry out the exploitation of the mobile device such as smart mobile phone or tablet device ardently, and expect that its market increases.In the field of the mobile devices such as such smart mobile phone or tablet device, existing because of impact or drop and the problem that causes the glass substrate in display etc. to split, this problem can not be ignored along with the universal of mobile device.And, in order to solve such problem, have studied the glass substrate of the glass manufacture mobile device that use is more difficult to split or thicken further to promote the countermeasures such as intensity by glass substrate itself.But, these countermeasures can produce productivity when reducing glass processing, increase the weight (reduction portability) of mobile device because thickness increases, further, because volume shared by battery is narrowing and makes the problems such as continuous operation time (driving time) cripetura.In such a case, in mobile device etc. utilizes the field of glass substrate, seek that there is high light transmittance as glass and the highest thermostability, and the appearance of material light and soft as resin film.

Here, as having high-fire resistance and soft raw material, it is known to polyimides.And, in such polyimides, such as, known aromatic polyimide (trade name " kapton (Kapton) " that DuPont manufactures) has sufficient flexibility as macromolecular material and has high-fire resistance, or raw material indispensable in the industry of the forward position such as space, flight use.Such aromatic polyimide is aromatic tetracarboxylic acid's dianhydride good to rigidity and symmetry and aromatic diamine to be synthesized, in display macromolecular material, the thermostability (glass transition temperature (Tg): 410 DEG C) of highest ranking is (with reference to engineering plastics, the most vertical publication, 1987, p88 (non-patent literature 1)).But, such aromatic polyimide is owing to can produce electric charge transfer (CT) between tetracarboxylic dianhydride's unit of aromatic rings class and the diamine unit of aromatic rings class, therefore, brown is presented, it is impossible to for needing the glass of light transmission to substitute purposes and optical applications etc..Therefore, seek to have the highest thermostability and can be used in glass and substitute the appearance of the polyimides with abundant light transmission in purposes etc., being conceived to not occur the exploitation of the ester ring type polyimides of intramolecular CT.

As the method manufacturing such ester ring type polyimides, generally use to combine ester ring type tetracarboxylic dianhydride and aromatic diamine and generate polyamic acid in a solvent, obtain polyamic acid (polyamideacid, polyamicacid) containing after liquid (polyamide acid varnish), directly on substrate etc., this is contained liquid masking, after being dried, in higher temperature { such as, as heating-up temperature during imidizate, generally use the high temperature (about 400 DEG C) of more than glass transition temperature } under heating carry out imidizate to manufacture the method (so-called hot-imide method) of polyimides.But, in ester ring type polyimide structures, its decomposition temperature is less than aromatic polyimide, and oxygen resistence is poor, therefore, the heating-up temperature of high temperature can become the reason of coloring, thus the manufacture method of common ester ring type polyimides not necessarily can manufacture the polyimides that suppressed sufficiently coloring.

It addition, as the manufacture method of ester ring type polyimides, it would however also be possible to employ utilize the chemical imidization method of so-called acid imide agent.But, for this chemical imidization method, from the viewpoint of thermostability, in the case of using rigidity and the good ester ring type tetracarboxylic dianhydride of symmetry as monomer, there is such ester ring type tetracarboxylic dianhydride and result from molecular structure and dissolubility is low, therefore, generally obtaining in the case of polyamic acid (polyamicacid) adds acid imide agent containing liquid, polyimides separates out unevenly, carry out imidizate, thus form the problem that uneven polyimides contains liquid (polyimide varnish).Therefore, in the manufacture method of ester ring type polyimides, the system that can use the chemical imidization method utilizing so-called acid imide agent is restricted to use soft and lose symmetric acid dianhydride as ester ring type tetracarboxylic dianhydride, the system of the dissolubility excellence this acid dianhydride and aromatic diamine being applied in combination is (such as, with reference to newly order up-to-date polyimides～basis and application～, NTS publishes, 2010,4th chapter, the filming condition of polyimides and film physical property, p76 (non-patent literature 2)).As such, it is possible to it is soft situation that the existing ester ring type polyimides using common chemical imidization method and obtaining is defined to utilizable monomer, the aspect at thermostability is set out the most abundant.

On the other hand, as having ester ring type polyimides and the manufacture method thereof of high light transmittance and thermostability, No. 2011/099518 pamphlet of International Publication (patent documentation 1) discloses polyimides and the manufacture method thereof with the repetitive described in specific formula.It addition, the method using the hot-imide carrying out imidizate under the heating-up temperature of about 250 DEG C in this embodiment hurdle described in patent documentation 1.But, even this manufacture method described in patent documentation 1, effectively and positively manufacture with lower temperature heating there is the highest light transmission and the polyimides of the highest thermostability in terms of also may not be abundant.

Prior art literature

Patent documentation

Patent documentation 1: No. 2011/099518 pamphlet of International Publication

Non-patent literature

Non-patent literature 1: engineering plastics, the most vertical publication, distribution in 1987, p88

Non-patent literature 2: newly order up-to-date polyimides～basis and application～,～NTS publishes, 2010, the 4th chapter, the filming condition of polyimides and film physical property, p76

Summary of the invention

Invent technical problem to be solved

The present invention is the technical problem being had in view of described prior art, its object is to provide and can utilize chemical imidization method and the ester ring type polyimides with the highest thermostability can be manufactured, the polyimides of abundant flexibility can be had with relatively low-temperature heat and manufacture, can more reliably prevent polyimides coloring when manufacturing, and the heating-up temperature of more low temperature can be used more effectively and positively to manufacture and have the highest light transmission, the manufacture method of the polyimides of the polyimides of the highest thermostability and sufficient flexibility, and by the polyimides obtained by this manufacture method.

Solve the means of technical problem

The present inventors attentively study, its result to reach described purpose, first obtain following opinion.That is, as it has been described above, the manufacture method of common polyimides there is utilization heat polyamic acid (polyamicacid) dehydration closed-loop is obtained the hot-imide method of polyimides；With the chemical imidization method by carrying out chemically dehydration closed-loop in acid imide agent addition polyamic acid (polyamicacid).The present inventors, first from the viewpoint of manufacturing polyimides with the heating of more low-temperature region, have studied and utilize the so-called chemical imidization method utilizing acid imide agent.But, use rigidity and the good ester ring type tetracarboxylic dianhydride of symmetry as monomer to obtain thermostability in the case of, even if directly utilizing existing acid imide agent (such as, acetic anhydride or pyridine etc.) attempt forming polyimides, substantially can separate out polyimides in solution and carry out imidizate again, the polyimides also becoming uneven contains liquid (uneven polyimide varnish).Therefore, further study the kind etc. of acid imide agent used in the case of using as monomer using the ester ring type tetracarboxylic dianhydride that rigidity and symmetry are good, result present inventors found that, such as, in using conventionally used acetic anhydride and/or the pyridine system as acid imide agent, if acid imide agent is added in the solution (polyamic acid contains liquid) containing polyamic acid, then according to circumstances can separate out the solution that polyimides becomes uneven, or, even if obtaining uniform solution (in this case, in this solution, polyamic acid and polyimides coexist sometimes) in the case of, in order to seek sufficient imidizate be also required to comparison high at a temperature of heating, the polyimides with abundant flexibility cannot be obtained with the heating condition of relatively low temperature, obtained polyimides is highly brittle.Additionally, contain in the case of liquid is uneven solution at polyamic acid, it is difficult to be coated with and obtains uniform colorless and transparent film, on the other hand, even if containing in the case of liquid (containing part polyimides) is uniform solution adding the polyamic acid after acid imide agent, also being difficult under low-temperature heat pass through the thin film that casting process etc. obtains having abundant flexibility, obtained polyimides is also not enough from the viewpoint of industrial utilization.So understand, from the viewpoint of the thermostability of polyimides, in the case of the ester ring type tetracarboxylic dianhydride good using rigidity and symmetry uses as monomer, even if utilizing merely so-called acid imide agent, the most also it is difficult to obtain uniform colorless and transparent film because separating out polyimides, additionally, even if containing in the case of liquid (containing part polyimides) is uniform solution adding the polyamic acid after acid imide agent, in order to be allowed to imidizate to manufacture the polyimides with abundant flexibility by heating process, this heating process is also required to higher temperatures (such as, degree more than 300 DEG C) heat.And, when implementing such high-temperature heating, may not be substantially prevented from resulting from the coloring of the polyimides of this heating-up temperature.So understand, in the case of using rigidity and the good ester ring type tetracarboxylic dianhydride of symmetry as monomer, when the existing acid imide agent of simple use, even if it is uniform solution that the polyamic acid after such as adding acid imide agent contains liquid (containing part polyimides), also may not necessarily be (different according to monomer with the heating condition of relatively low temperature, degree (the more preferably degree of less than 250 DEG C of such as less than 300 DEG C, the degree of more preferably less than 200 DEG C) heating condition) fully carry out imidizate, obtained polyimides tends to crisp and does not has flexibility, may not manufacture and there is desired characteristic (sufficient flexibility, the highest light transmission and the highest thermostability) polyimides.

Additionally, the ester ring type polyimides high in order to obtain thermostability, do not utilize imidizate agent and merely with hot-imide method in the case of, as heating-up temperature, such as, although different according to monomer, if but use the low temperature of the degree less than 200 DEG C, then compare and polyamic acid (polyamicacid) dehydration closed-loop is formed the reaction of polyimides, polyamic acid is decomposed into acid dianhydride and tends to become favourable with the balancing response of amine.Therefore, in the case of merely with hot-imide method, in order to more reliably manufacture the transparency and the high polyimides of thermostability, need to implement the heating process than higher temperatures as existing method.

Based on above opinion, the present inventors the most attentively study, found that, by using the polyamic acid containing the repetitive having represented by following formula (1), halogen carboxylic acid anhydrides and the mixture of aliphatic category tertiary amine, by described polyamic acid imidizate, chemical imidization method can be utilized surprisingly and the polyimides of the ester ring type with the highest thermostability can be manufactured, the polyimides with abundant flexibility can be manufactured with the heating of relatively low temperature, can more reliably prevent polyimides coloring when manufacturing, and the heating-up temperature of more low temperature can be used more effectively and positively to manufacture and have the highest light transmission, the highest thermostability and the polyimides of sufficient flexibility, thus complete the present invention.

I.e., the manufacture method of the polyimides of the present invention is that use contains: have the polyamic acid of repetitive represented by following formula (1), halogen carboxylic acid anhydrides and the mixture of aliphatic category tertiary amine, by by described polyamic acid imidizate, thus the method obtaining there is the polyimides of the repetitive represented by following formula (2).

[in formula (1), R¹Represent and replace the group in basic group, R selected from the tetravalence represented by following formula (I-1)～(I-10)²Represent the group in the bivalent substituted basic group represented by following formula (II-1)～(II-4).]

(in formula, R³Representing the one in the alkyl that hydrogen atom, carbon number are 1～10 and fluorine atom independently of one another, Q represents selected from formula :-O-,-S-,-CO-,-CONH-,-SO₂-、-C(CF₃)₂-、-C(CH₃)₂-、-CH₂-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-O-C₆H₄-SO₂-C₆H₄-O-、-C(CH₃)₂-C₆H₄-C(CH₃)₂-、-O-C₆H₄-C₆H₄-O-and-O-C₆H₄The one in group represented by-O-.)

[in formula (2), R¹And R²Respectively with the R in described formula (1)¹And R²Identical meanings.]

In the manufacture method of the polyimides of the invention described above, the operation of described polyamic acid imidizate will be preferably included in the operation heating described mixture at a temperature of lower than the glass transition temperature of described polyimides 80～300 DEG C.

It addition, in the manufacture method of the polyimides of the invention described above, in described mixture, be 1 mole relative to the repetitive of described polyamic acid, the content ratio of described halogen carboxylic acid anhydrides is preferably 0.01～4.0 mole.

Further, in the manufacture method of the polyimides of the invention described above, in described mixture, being 1 mole relative to the repetitive of described polyamic acid, the content ratio of described aliphatic category tertiary amine is preferably 0.01～4.0 mole.

Additionally, in the manufacture method of the polyimides of the invention described above, preferably further include by making the tetracarboxylic dianhydride represented by following formula (3) react with the aromatic diamine represented by following formula (4) in organic solvent, thus obtain the operation of described polyamic acid.

[in formula (3), R¹With the R in described formula (1)¹Identical meanings.]

H₂N-R²-NH₂(4)

[in formula (4), R²With the R in described formula (1)²Identical meanings.]

Additionally, in the manufacture method of the polyimides of the invention described above, described halogen carboxylic acid anhydrides is preferably selected from trifluoroacetic anhydride, difluoroacetic acid acid anhydride, Fluoroethanoic acid acid anhydride, PFPA, heptafluorobutyric anhydride, Trichloroacetic anhydride, dichloroacetic acid acid anhydride, monochloroacetic acid anhydride, tribromoacetic acid acid anhydride, dibromoacetic acid acid anhydride, bromoacetic acid acid anhydride, chlorine difluoroacetic acid acid anhydride, chlorine tetrafluoro propionic andydride, chlorine hexafluoro butyryl oxide. and formed these acid anhydrides acid mixed acid anhydride at least one, more preferably selected from trifluoroacetic anhydride, PFPA, heptafluorobutyric anhydride and formed these acid anhydrides acid mixed acid anhydride at least one.

It addition, in the manufacture method of the polyimides of the invention described above, described aliphatic category tertiary amine is preferably the tertiary amine represented by following formula (5).

[in formula (5), R³Represent the alkyl that carbon number is 1～10 independently of one another.]

Represented tertiary amine.

The polyimides of the present invention be by the manufacture method of the polyimides of the invention described above obtained by polyimides.

The effect of invention

According to the present invention, can provide and can utilize chemical imidization method and the ester ring type polyimides with the highest thermostability can be manufactured, the polyimides with abundant flexibility can be manufactured with the heating of relatively low temperature, can more reliably prevent polyimides coloring when manufacturing, and the heating-up temperature that can use more low temperature is come more effectively and positively manufactures the manufacture method of polyimides of the polyimides with the highest light transmission, the highest thermostability and sufficient flexibility, and by the polyimides obtained by this manufacture method.

Accompanying drawing explanation

Fig. 1 is the curve chart of the IR spectrum representing the composition (reprecipitation thing) in the mixture obtained in embodiment 1.

Fig. 2 is to represent the composition (reprecipitation thing) in the mixture obtained in embodiment 1¹The curve chart of H-NMR spectrum.

Fig. 3 is by shown in Fig. 2¹The curve chart amplified near 6ppm～13ppm of H-NMR spectrum.

Fig. 4 is the curve chart of the IR spectrum representing the polyimides (thin film) obtained in embodiment 1.

Fig. 5 is to represent the polyimides (thin film) obtained in embodiment 1¹The curve chart of H-NMR spectrum.

Fig. 6 is by shown in Fig. 5¹The curve chart amplified near 6ppm～13ppm of H-NMR spectrum.

Fig. 7 is the curve chart of the IR spectrum representing the composition (reprecipitation thing) in the mixture obtained in embodiment 2.

Fig. 8 is to represent the composition (reprecipitation thing) in the mixture obtained in embodiment 2¹The curve chart of H-NMR spectrum.

Fig. 9 is by shown in Fig. 8¹The curve chart amplified near 6ppm～13ppm of H-NMR spectrum.

Figure 10 is the curve chart of the IR spectrum representing the polyimides (thin film) obtained in embodiment 2.

Figure 11 is to represent the polyimides (thin film) obtained in embodiment 2¹The curve chart of H-NMR spectrum.

Figure 12 is by shown in Figure 11¹The curve chart amplified near 6ppm～13ppm of H-NMR spectrum.

Detailed description of the invention

Below preferred embodiment to explain the present invention.

[manufacture method of polyimides]

The manufacture method of the polyimides of the present invention is illustrated.As mentioned above, the manufacture method of the polyimides of the present invention is that use contains: have the polyamic acid of repetitive represented by described formula (1), halogen carboxylic acid anhydrides and the mixture of aliphatic category tertiary amine, by by described polyamic acid imidizate, thus the method obtaining there is the polyimides of the repetitive represented by described formula (2).

Additionally, manufacture method by the polyimides of such present invention, even if heat with the temperature field of more low temperature during fabrication can also manufacture efficiently there is desired characteristic (sufficient flexibility, the highest light transmission and the highest thermostability) though the reason of polyimides clear and definite, but the present inventors are inferred as following reason.I.e., in the present invention, described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine first it are applied in combination.By use combined as described above described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, thus the most described halogen carboxylic acid anhydrides plays the effect as dehydrant, described aliphatic category tertiary amine plays the effect as dehydration accelerator, carries out the part imidizate of described polyamic acid (polyamicacid).Even if it addition, carry out such part imidizate, in the case of described mixture contains solvent, polyimides owing to being formed dissolves in the described solvent used by polyreaction, thus, the precipitation (precipitation) of polyimides also will not occur, uniform mixture can be obtained.Secondly, in the case of heating such uniform mixture with cryogenic conditions, described halogen carboxylic acid anhydrides in mixture and described aliphatic category tertiary amine play catalytic action, thus the imidizate of described polyamic acid can be carried out in described mixture efficiently, manufacture the polyimides with desired characteristic (sufficient flexibility, the highest light transmission and the highest thermostability).At this, if simpling illustrate the manufacture of polyimides in case of the polyimides forming film like, described polyamic acid (polyamicacid) can be obtained the most as mentioned above by the uniform mixture of part imidizate such that it is able to be cast equably (casting masking) by described mixture.Then, in the case of by the dried coating film after this casting masking, the uniform thin film (dry coating) being made up of the mixture of polyamic acid (polyamicacid) Yu polyimides with the highest light transmission can be manufactured.Then, in this dry coating, play catalytic action owing to remaining in the described halogen carboxylic acid anhydrides in film and described aliphatic category tertiary amine, therefore, even if carrying out heating with low temperature can also be sufficiently carried out imidizate.As it has been described above, the present invention with the easiest method, and can have the polyimides of desired characteristic (sufficient flexibility, the highest light transmission and the highest thermostability) by the heating process manufacture of low temperature.As mentioned above, in the present invention owing to the part imidizate by chemical imidization method produced in mixture and the heat by heating then, chemistry the imidizate of usage can be utilized, therefore, it can the heating with more low temperature and manufacture polyimides efficiently.Being additionally, since in the present invention when manufacturing can be with the heating of more low temperature to manufacture polyimides, accordingly it is also possible to manufacture equipment more easily with easier operation and utilization to manufacture polyimides.Therefore, from the viewpoint of industrialization, reducing cost (economy), the manufacture method of the polyimides of the present invention can be described as the method for excellence.Additionally, by using described mixture to manufacture polyimides, thus the heating process (without using existing hot-imide method) of the higher temperatures (such as more than 300 DEG C) of the reason of coloring can be become without enforcement, accordingly it is also possible to more fully and more reliably prevent the coloring of obtained polyimides.Therefore, in the case of using described mixture, the Kapton with the highest light transmission can be manufactured efficiently.From such a viewpoint, the present inventors infer the manufacture method of the polyimides by the present invention, even if during fabrication in the case of implementing the heating of temperature field of more low temperature, it is also possible to manufacture the polyimides with desired characteristic (sufficient flexibility, the highest light transmission and the highest thermostability) efficiently.

First below each composition used in the present invention is illustrated.

(polyamic acid)

Polyamic acid involved in the present invention is illustrated.This polyamic acid is the polyamic acid represented by following formula (1).

In this formula (1), R¹For replacing the group in basic group selected from the tetravalence represented by following formula (I-1)～(I-10).As such R¹From the viewpoint of thermostability, the transparency, linear expansion coefficient, intensity, it is preferably selected from the group in following formula (I-1), (I-3), (I-9) and (I-10), more preferably the group in following formula (I-9) and (I-10).

It addition, in above-mentioned formula (1), R²For the group in the bivalent substituted basic group represented by following formula (II-1)～(II-4).

In this formula (II-3), R³It is each independently the one in the alkyl that hydrogen atom, carbon number are 1～10 and fluorine atom.As such R³, from the viewpoint of thermostability, more preferably hydrogen atom, fluorine atom, methyl or ethyl, particularly preferably hydrogen atom.

It addition, in above-mentioned formula (II-4), Q is selected from formula :-O-,-S-,-CO-,-CONH-,-SO₂-、-C(CF₃)₂-、-C(CH₃)₂-、-CH₂-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-O-C₆H₄-SO₂-C₆H₄-O-、-C(CH₃)₂-C₆H₄-C(CH₃)₂-、-O-C₆H₄-C₆H₄-O-and-O-C₆H₄The one in group represented by-O-.As such Q, from the viewpoint of thermostability with deliquescent balance, preferably formula :-O-C₆H₄-O-、-O-、-C(CH₃)₂-、-CH₂-or-O-C₆H₄-C(CH₃)₂-C₆H₄Group represented by-O-, particularly preferably formula :-O-C₆H₄Group represented by-O-or-O-.

It addition, as the R can being chosen as in above-mentioned formula (1)²Formula (II-1)～(II-4) represented by group, it is the highest temperature and to make linear expansion coefficient be substantially low value from glass transition temperature can be made, the balance of these characteristics can be promoted, from the viewpoint of obtaining higher thermostability, more preferably formula (II-3) or the group represented by (II-4).

Further, R²In, from making, linear expansion coefficient is lower, from the viewpoint of obtaining higher thermostability, and the preferably group represented by formula (II-3)；Or group and the described Q represented by formula (II-4) is-CONH-,-COO-,-CO-,-C₆H₄At least one in-represented group (the more preferably group represented by-CONH-or-COO-, the particularly preferably group represented by-CONH-).

It addition, as R², from the viewpoint of the polyimides obtained by higher pliability (flexibility) (flexibility) can being given, the preferably group represented by formula (II-1)；Or group and the described Q represented by formula (II-4) is-O-,-S-,-CH₂-、-O-C₆H₄At least one (more preferably-O-,-CH in group represented by-O-₂One in-represented group, the more preferably group represented by-O-).

As described polyamic acid, from the viewpoint of can giving the highest glass transition temperature, substantially low linear expansion coefficient and sufficient pliability (flexibility) to obtained polyimides well with higher level and balance, preferably comprise multiple (more than two kinds) R²The repetitive represented by diverse formula (1).

As the polyamic acid of the repetitive having represented by such formula (1), intrinsic viscosity [η] is preferably 0.05～3.0dL/g, and more preferably 0.2～2.0dL/g, more preferably 0.4～1.5dL/g.If this intrinsic viscosity [η] is less than 0.05dL/g, then use it when manufacturing the polyimides of film like, to tend to obtained thin film to become fragile, on the other hand, if it exceeds 3.0dL/g, then viscosity is too high and reduce processability, thus is difficult to when tending to manufacture such as thin film obtain uniform thin film.It addition, this intrinsic viscosity [η] can be measured with following method.I.e., first, use N,N-dimethylacetamide as solvent, described polyamic acid is dissolved in this N,N-dimethylacetamide and makes concentration become 0.5g/dL, obtain measuring sample (solution).Then, use described mensuration sample, under the temperature conditions of 30 DEG C (such as, use the temperature chamber of 30 DEG C as the temperature conditions of 30 DEG C), use kinematic viscosimeter to measure the viscosity of described mensuration sample, the value tried to achieve is used as intrinsic viscosity [η].It addition, as this kinematic viscosimeter, use the automatic viscosity determinator (trade name " VMC-252 ") that clutch company manufactures.

Additionally, it is not particularly limited for manufacturing the operation of such polyamic acid, the operation that can manufacture the polyamic acid with repetitive above-mentioned formula (1) represented by be may be appropriately used, wherein, preferably employ by making the tetracarboxylic dianhydride represented by following formula (3) react with the aromatic diamine represented by following formula (4) in organic solvent, thus obtain the operation of described polyamic acid.I.e., in the manufacture method of the polyimides of the present invention, preferably further include obtaining the operation of described polyamic acid by making the tetracarboxylic dianhydride represented by described formula (3) react with the aromatic diamine represented by described formula (4).

[in formula (3), R¹With the R in described formula (1)¹Identical meanings.]

H₂N-R²-NH₂(4)

[in formula (4), R²With the R in described formula (1)²Identical meanings.]

Tetracarboxylic dianhydride used in such operation obtaining polyamic acid represents with above-mentioned formula (3), the R in this formula (3)¹With the R in described formula (1)¹Identical meanings (the R in formula (3)¹Preferred group and formula (1) in R¹Identical.).

nullAs the tetracarboxylic dianhydride represented by this formula (3)，Such as can enumerate norbornane-2-spiral shell-α-Ketocyclopentane-α '-spiral shell-2 "-norbornane-5,5”,6,6 "-tetracarboxylic dianhydride、Norbornane-2-spiral shell-α-Ketohexamethylene-α '-spiral shell-2 "-norbornane-5,5”6,6 "-tetracarboxylic dianhydride、1,2,3,4-Tetramethylene. tetracarboxylic dianhydride、1,2,3,4-Pentamethylene. tetracarboxylic dianhydride、1,2,4,5-cyclopentanetetracarboxylic's dianhydride、1,2,3,4-cyclopentanetetracarboxylic's dianhydride、2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride、3,5,6-tri-carboxyl norbornane-2-acetic acid dianhydride、2,3,4,5-oxolane tetracarboxylic dianhydride、1,3,3a,4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone、1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone、1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone、5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride、Bicyclo-[2,2,2]-octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride、Dicyclohexyl-3,3’,4,4 '-tetracarboxylic dianhydride、Bicyclo-[2,2,1]-heptane-2,3,5,6-tetracarboxylic dianhydride、Ditwistane-2,3,6,7-tetracarboxylic dianhydride、Ten dihydros-1,4:5,8-dimethylene anthracene-9,10-diketone-2,3:6,7-tetracarboxylic acid dianhydride etc..

It addition, the manufacture method of such tetracarboxylic dianhydride is not particularly limited, known method be may be appropriately used, for example, it is also possible to suitably use No. 2011/099518 method etc. described in pamphlet of International Publication.It addition, such tetracarboxylic dianhydride can also use commercially available product.

It addition, obtaining aromatic diamine used in the operation of described polyamic acid is the diamidogen represented by above-mentioned formula (4), the R in this formula (4)²With the R in described formula (1)²Identical meanings (the R in formula (4)²Preferred group and formula (1) in R²Identical.).

nullAs the aromatic diamine represented by this formula (4)，Such as can enumerate 4,4 '-diaminodiphenyl-methane、4,4 "-diaminourea-para-terpheny、3,3 '-diaminodiphenyl-methane、4,4 '-diamino-diphenyl ethane、3,3 '-diamino-diphenyl ethane、4,4 '-benzidine、3,3 '-benzidine、4,4 '-diamino-diphenyl ether、3,3 '-diamino-diphenyl ether、2,Double (4-aminophenoxy phenyl) propane of 2-、1,Double (4-amino-benzene oxygen) benzene of 3-、1,Double (3-amino-benzene oxygen) benzene of 3-、Double [4-(4-amino-benzene oxygen) phenyl] sulfone、Double [4-(3-amino-benzene oxygen) phenyl] sulfone、2,2 '-bis-(trifluoromethyls)-4,4 '-benzidine、3,4 '-diamino-diphenyl ether、4,4 '-diaminobenzophenone、3,3 '-diaminobenzophenone、9,Double (4-aminophenyl) fluorenes of 9-、Para diaminobenzene (another name: p-phenylenediamine)、Between diaminobenzene、Ortho-diaminobenzene、4,4 '-benzidine、3,3 '-benzidine、2,2 '-benzidine、3,4 '-benzidine、2,6-diaminonaphthalene、1,4-diaminonaphthalene、1,5-diaminonaphthalene、4,4’-[1,3-phenylene is double (1-methyl-ethylene)] dianil、4,4’-[1,4-phenylene is double (1-methyl-ethylene)] dianil、2,2 '-dimethyl-4,4 '-benzidine (another name: o-tolidine)、3,3 '-dimethyl-4,4 '-benzidine、3,3 '-diamino diphenyl sulfone、4,4 '-diamino diphenyl sulfone、4,4 '-diamino diphenyl sulfide、1,Double (4-amino-benzene oxygen) benzene of 4-、4,4 '-bis-(4-amino-benzene oxygen) biphenyl、4,4 '-diaminobenzene formailide、4,4 '-diamino-phenyl benzoate (another name: 4,4 '-diamino-diphenyl ester)、9,9 '-bis-(4-aminophenyl) fluorenes、O-tolidine sulfone、1,3 '-bis-(4-amino-benzene oxygens)-2,2-dimethylpropane、2,3,5,6-tetramethyl-1,4-phenylenediamine、3,3’,5,5 '-tetramethyl benzidine、1,Double (4-amino-benzene oxygen) pentane of 5-、Diethyl toluene diamine、Aminobenzyl amine、Dianil M (BisanilineM)、Dianil P etc..

It addition, as the method for manufacturing above-mentioned aromatic diamine, be not particularly limited, known method be may be appropriately used.It addition, described aromatic diamine can suitably use commercially available product.

Further, as obtaining organic solvent used in the operation of described polyamic acid, it is preferably capable dissolving the tetracarboxylic dianhydride represented by above-mentioned formula (3) and the organic solvent of the aromatic diamine represented by above-mentioned formula (4).As described organic solvent, such as can enumerate METHYLPYRROLIDONE, N, N-dimethyl acetylamide, N, the non-proton class polar solvent of dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, Allyl carbonate, tetramethylurea, DMI, HMPA, pyridine etc.；The phenol solvent of metacresol, xylenol, phenol, halogenated phenol etc.；The ether solvent of oxolane, dioxanes, cellosolve, glycol dimethyl ether (glyme) etc.；The aromatic series kind solvent etc. of benzene,toluene,xylene, 2-chloro-4-hydroxyl toluene etc..These organic solvents can be used alone one or mixing two kinds is used above.

Additionally, in the operation obtaining described polyamic acid, tetracarboxylic dianhydride represented by above-mentioned formula (3) is not particularly limited with the usage amount of the aromatic diamine represented by above-mentioned formula (4), and these mol ratio ([tetracarboxylic dianhydride]: [aromatic diamine]) preferably becomes 0.5:1.0～1.0:0.5 (more preferably 0.9:1.0～1.0:0.9).Tend to yield when the usage amount of described tetracarboxylic dianhydride is less than described lower limit reduce, on the other hand, exceed the described upper limit and also tend to yield reduction.

Additionally, in the operation obtaining described polyamic acid, use ratio for the tetracarboxylic dianhydride represented by above-mentioned formula (3) with the aromatic diamine represented by above-mentioned formula (4), the amino being had relative to the aromatic diamine represented by above-mentioned formula (4) is 1 equivalent, the anhydride group making the tetracarboxylic dianhydride represented by above-mentioned formula (3) is preferably 0.2～2 equivalents, more preferably 0.3～1.2 equivalents.When this use ratio is less than described lower limit, it is impossible to effectively carry out polyreaction, it is intended to the polyamic acid of high molecular cannot be obtained, on the other hand, if it exceeds the described upper limit, tend to obtain the polyamic acid of high molecular the most as described above.

Further, as the usage amount of the described organic solvent in the operation obtaining described polyamic acid, the total amount of the tetracarboxylic dianhydride represented by above-mentioned formula (3) and the aromatic diamine represented by above-mentioned formula (4) preferably becomes the amount of 0.1～50 mass % (more preferably 10～30 mass %) relative to the total amount of reaction solution.When the usage amount of described organic solvent is less than described lower limit, it is intended to polyamic acid cannot be efficiently obtained by, on the other hand, if it exceeds the described upper limit, then tend to be difficult to stir because of high viscosity.

Additionally, in the operation obtaining described polyamic acid, from the viewpoint of promoting response speed when making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react with the aromatic diamine represented by above-mentioned formula (4) and obtaining the polyamic acid of high polymerization degree, it is also possible to add alkali cpd in described organic solvent further.As described alkali compounds, be not particularly limited, such as can enumerate triethylamine, tri-butylamine, three hexyl amines, 1,8-diazabicylo [5.4.0]-hendecene-7, pyridine, isoquinolin, N-methyl piperidine, α-methylpyridine etc..It addition, the usage amount of described alkali cpd is preferably 0.001～10 equivalents, more preferably 0.01～0.1 equivalent relative to the tetracarboxylic dianhydride represented by the above-mentioned formula (6) of 1 equivalent.Tend to find additive effect, on the other hand, if it exceeds the described upper limit then tends to the reason of coloring etc. when the usage amount of described alkali cpd is less than described lower limit.

Additionally, in the operation obtaining described polyamic acid, reaction temperature when making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react with the aromatic diamine represented by above-mentioned formula (4) can suitably be adjusted to the temperature that these compounds can be made to react, it is not particularly limited, it is preferably less than 80 DEG C, more preferably-30～30 DEG C.Additionally, as obtaining the method making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react that can use in the operation of described polyamic acid with the aromatic diamine represented by above-mentioned formula (4), the known method that can carry out tetracarboxylic dianhydride with the polyreaction of aromatic diamine be may be appropriately used.Such as, can use after making described aromatic diamine be dissolved in solvent under the inert atmosphere of nitrogen, helium, argon etc. in atmospheric pressure, the tetracarboxylic dianhydride represented by above-mentioned formula (3), thereafter, the method being allowed to react 10～48 hours is added under described reaction temperature.Tend to be difficult to be sufficiently carried out reaction when described reaction temperature and response time are less than described lower limit, on the other hand, if it exceeds the described upper limit then can tend to improve being mixed into probability and reduce molecular weight of material (steam etc.) making polymer deterioratoin.

As mentioned above, by making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react with the aromatic diamine represented by above-mentioned formula (4), the polyamic acid with the repetitive represented by above-mentioned formula (1) of at least one can be obtained.Additionally, the polyamic acid of the thus obtained repetitive having represented by above-mentioned formula (1) can be isolated after as using for forming the ingredients of a mixture involved in the present invention, or do not separate and there is the polyamic acid of the repetitive represented by above-mentioned formula (1) and directly utilize the reactant liquor (reactant liquor of the polyamic acid containing the repetitive having represented by above-mentioned formula (1)) obtained by making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react with the aromatic diamine represented by above-mentioned formula (4) in organic solvent, using the state that is present in this reactant liquor as using for forming the ingredients of a mixture involved in the present invention.Additionally, in the case of using after separating the polyamic acid with the repetitive represented by above-mentioned formula (1) from described reactant liquor, this separation method is not particularly limited, the known method that polyamic acid can be separated be may be appropriately used, it is for instance possible to use the method etc. separated as reprecipitation thing.

(halogen carboxylic acid anhydrides)

Halogen carboxylic acid anhydrides involved in the present invention is illustrated.In the present invention, in order to manufacture the polyimides under the heating of relatively low temperature with abundant flexibility, chemically show the reactivity (condensation) of appropriateness during imidizate, from the viewpoint of obtaining imide ring closure activity with (during solidification) during relatively low-temperature heat, halogen carboxylic acid anhydrides can be used with aliphatic category tertiary amine combinations.Even if by the compound beyond described halogen carboxylic acid anhydrides and aliphatic category tertiary amine combinations, the reactivity (condensation) of appropriateness is not the most shown when chemical imidization, so that imide ring closure activity also cannot be obtained during relatively low-temperature heat, thus the most soft and that light transmission is high polyimides cannot be manufactured.

Here, halogen carboxylic acid anhydrides refers to the compound { compound that halogen substiuted aliphatic group (aliphatic group that at least 1 hydrogen atom is substituted with halogen atoms) is combined into carboxylic acid anhydride group } that carboxylic acid anhydride group is combined into the aliphatic group containing at least 1 halogen atom.So, as halogen carboxylic acid anhydrides involved in the present invention, from the reactivity of appropriateness, the imide ring closure activity of appropriateness, from the viewpoint of volatility, it is possible to use the compound that the aliphatic group (halogen atom replacement aliphatic group) that at least 1 hydrogen atom is substituted with halogen atoms is combined into carboxylic acid anhydride group.

Additionally, as halogen atom contained in described halogen carboxylic acid anhydrides, from the viewpoint of the reactivity of appropriateness, the imide ring closure activity of appropriateness, volatility, preferably fluorine atom, chlorine atom, bromine atoms, more preferably fluorine atom, chlorine atom, particularly preferably fluorine atom.It addition, replace straight-chain alkyl that the aliphatic group in aliphatic group, preferably carbon number are 1～5 as described halogen atom, carbon number is the branched-chain alkyl of 3～5, more preferably carbon number is the straight-chain alkyl of 1～3.

nullAdditionally，In described halogen carboxylic acid anhydrides，Reactivity from appropriateness、The imide ring closure activity of appropriateness、From the viewpoint of volatility，It is preferably selected from trifluoroacetic anhydride、Difluoroacetic acid acid anhydride、Fluoroethanoic acid acid anhydride、PFPA、Heptafluorobutyric anhydride、Trichloroacetic anhydride、Dichloroacetic acid acid anhydride、Monochloroacetic acid anhydride、Tribromoacetic acid acid anhydride、Dibromoacetic acid acid anhydride、Bromoacetic acid acid anhydride、Chlorine difluoroacetic acid acid anhydride、Chlorine tetrafluoro propionic andydride、Chlorine hexafluoro butyryl oxide.、And form these acid anhydride (trifluoroacetic anhydride、Difluoroacetic acid acid anhydride、Fluoroethanoic acid acid anhydride、PFPA、Heptafluorobutyric anhydride etc.) acid (trifluoroacetic acid、Difluoroacetic acid、Fluoroethanoic acid、Five fluorine propanoic acid、Hyptafluorobutyric acid etc.) mixed acid anhydride at least one，More preferably selected from trifluoroacetic anhydride、PFPA、Heptafluorobutyric anhydride and formed these acid anhydrides acid mixed acid anhydride at least one，More preferably selected from trifluoroacetic anhydride、PFPA and formed these acid anhydrides acid mixed acid anhydride at least one.It addition, " mixed acid anhydride " mentioned here refer to by two kinds of halogen carboxylic acid dehydrating condensations obtained by anhydride.Further, in these halogen carboxylic acid anhydrides, more preferably trifluoroacetic anhydride, PFPA, heptafluorobutyric anhydride, particularly preferably trifluoroacetic anhydride, PFPA.It addition, these halogen carboxylic acid anhydrides can be used alone one or can also two kinds of combination of the above be used.

As the method for manufacturing described halogen carboxylic acid anhydrides, it is not particularly limited, known method be may be appropriately used.It addition, described halogen carboxylic acid anhydrides can also suitably use commercially available product.

(aliphatic category tertiary amine)

Aliphatic category tertiary amine involved in the present invention is illustrated.In the present invention, from the viewpoint of the reactivity of appropriateness, the imide ring closure activity of appropriateness, volatility, described aliphatic category tertiary amine is applied in combination with described halogen carboxylic acid anhydrides.Even if the compound beyond described aliphatic category tertiary amine is combined with described halogen carboxylic acid anhydrides, the most do not show the reactivity of appropriateness, the imide ring closure activity of appropriateness, volatility, thus the most soft and that light transmission is high polyimides cannot be manufactured.

Described aliphatic category tertiary amine is preferably the compound represented by following formula (5).

[in formula (5), R³Represent aliphatic group independently of one another.]

R in described formula (5)³Can be identical or different, aliphatic group can be respectively.As being utilized as described R³Aliphatic group, from the reactivity of appropriateness, the imide ring closure activity of appropriateness, from the viewpoint of volatility, preferably carbon number be 1～10 straight-chain aliphatic group, carbon number be 1～10 branched aliphatic group.It addition, R³The most independent more preferably carbon number is the alkyl of 1～5, and particularly preferably carbon number is the alkyl of 1～2.If it addition, the carbon number of described alkyl is beyond the described upper limit, then tend to not show the reactivity of appropriateness, the imide ring closure activity of appropriateness, volatility.

Additionally, as described aliphatic category tertiary amine, such as can enumerate Trimethylamine, triethylamine, tripropylamine, triisopropylamine, diisopropyl ethyl amine, tri-butylamine, three amylamines, DBU, DBN, DABCO, from the viewpoint of the reactivity of appropriateness, the imide ring closure activity of appropriateness, volatility, wherein, more preferably Trimethylamine, triethylamine, tripropylamine, triisopropylamine, diisopropyl ethyl amine, more preferably Trimethylamine, triethylamine, diisopropyl ethyl amine.It addition, described aliphatic category tertiary amine can be used alone one or can also two kinds of combination of the above be used.

As the method for manufacturing described aliphatic category tertiary amine, it is not particularly limited, known method be may be appropriately used.It addition, described aliphatic category tertiary amine can also suitably use commercially available product.

(mixture)

Then, mixture involved in the present invention is described.Mixture involved in the present invention is for containing having the polyamic acid of repetitive represented by described formula (1), described halogen carboxylic acid anhydrides and the mixture of described aliphatic category tertiary amine.So, in mixture involved in the present invention, select from so-called acid imide agent described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine combine containing.So, owing to described mixture selects and be applied in combination described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, therefore, although its reason is the clearest and the most definite, even if it is (different according to monomer with relatively low temperature, the low temperature of the degree of such as less than 300 DEG C, it is preferably the low temperature of the degree of less than 250 DEG C, the more preferably low temperature of the degree of less than 230 DEG C, the low temperature of the degree of more preferably less than 210 DEG C) heat and can also manufacture, efficiently by described polyamic acid imidizate, the ester ring type polyimides that light transmission is the highest efficiently.

Described mixture, from easy to apply, from the viewpoint of promoting processing characteristics further, it is also possible to containing organic solvent.As this organic solvent, be preferably used with as the identical organic solvent obtained illustrated by organic solvent used in the operation of described polyamic acid.Additionally, described mixture is not particularly limited, from the viewpoint of the manufacture efficiency promoting polyimides, can be preferably by: use the operation obtaining described polyamic acid, after making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react with the aromatic diamine represented by above-mentioned formula (4) and obtain reactant liquor (containing the reactant liquor of the polyamic acid with repetitive represented by above-mentioned formula (1)) in organic solvent, directly use this reactant liquor, add described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine to mixture obtained by described reactant liquor.

It addition, in described mixture, be 1 mole relative to the repetitive of described polyamic acid, the content ratio of the described halogen carboxylic acid anhydrides in this mixture is preferably 0.01～4.0 mole (more preferably 0.1～3.0, more preferably 0.2～2.0).When the content ratio of described halogen carboxylic acid anhydrides is less than described lower limit, not sufficiently effective (additive effect reduction) obtained by tending to by the described halogen carboxylic acid anhydrides of interpolation, on the other hand, if it exceeds the described upper limit, then can become the reason that polymer precipitation occurs in mixture, it is intended to mixture becomes uneven.If it addition, described mixture is uneven, then will be unable to be cast (casting masking) equably.Then, time by dried coating film after this casting masking, it is impossible to manufacturing the thin film (dry coating) being made up of uniformly the mixture of polyamic acid Yu polyimides, result cannot obtain transparent and uniform thin film.

Additionally, in mixture involved in the present invention, being 1 mole relative to the repetitive of described polyamic acid, the content ratio of the described aliphatic category tertiary amine in this mixture is preferably 0.01～4.0 mole (more preferably 0.1～3.0, more preferably 0.2～2.0).When the content ratio of described aliphatic category tertiary amine is less than described lower limit, not sufficiently effective (additive effect reduction) obtained by tending to by the described aliphatic category tertiary amine of interpolation, on the other hand, if it exceeds the described upper limit, then can become the reason that polymer precipitation occurs in mixture, it is intended to mixture becomes uneven.

During it addition, described mixture contains organic solvent, the content of the described polyamic acid in described mixture is preferably 1～50 mass %, more preferably 10～30 mass %.When the content of this polyamic acid is less than described lower limit, it is intended to cannot be sufficiently carried out chemical imidization reaction in the mixture, on the other hand, exceed the described upper limit to remain on and tend to be sufficiently carried out chemical imidization reaction.

Additionally, as the method manufacturing described mixture, it is not particularly limited, can use: use the operation obtaining described polyamic acid, after making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react with the aromatic diamine represented by above-mentioned formula (4) and obtain reactant liquor (containing the reactant liquor of the polyamic acid with repetitive represented by above-mentioned formula (1)) in organic solvent, directly use this reactant liquor, add described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine to method (A) in described reactant liquor；Or use the operation obtaining described polyamic acid, after obtaining the reactant liquor of polyamic acid containing the repetitive having represented by above-mentioned formula (1), described polyamic acid is separated from described reactant liquor, thereafter, polyamic acid after separating is dissolved in organic solvent, obtain the lysate containing polyamic acid, then add described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine to method (B) in this lysate.It addition, in said method, from the viewpoint of polyimides is made more efficiently, it is preferred to use said method (A).

Additionally, in the manufacture method of described mixture, liquid (described reactant liquor or described lysate) is contained relative to the polyamic acid containing described polyamic acid, the order adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine is not particularly limited, can add simultaneously, but after preferably adding described aliphatic category tertiary amine, add described halogen carboxylic acid anhydrides.By adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine with such order, thus the reactivity (condensation) of appropriateness is shown when chemical imidization, can obtain imide ring closure activity with (during solidification) during relatively low-temperature heat, result can manufacture the polyimides with abundant flexibility with lower temperature heating.

It addition, in the manufacture method of described mixture, as adding described halogen carboxylic acid anhydrides and atmospheric condition during described aliphatic category tertiary amine, it is not particularly limited, can be the common chemical imidization condition such as enforcement under the noble gas of nitrogen etc..It addition, in the manufacture method of described mixture, as adding described halogen carboxylic acid anhydrides and temperature conditions during described aliphatic category tertiary amine, be not particularly limited, be preferably-30 DEG C～80 DEG C, more preferably 0 DEG C～60 DEG C.When described temperature conditions is less than described lower limit, viscosity promotes or occurs solidification to tend to stir, on the other hand, if it exceeds the described upper limit, then tend to homogenize or occur molecular weight to reduce because the fracture of the amido link of polyamic acid along with precipitating the inequality caused because polyimides generates.It addition, in order to meet described temperature conditions, such as the described polyamic acid that can be cooled with an ice bath contains liquid (described reactant liquor or described lysate) and adds described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine.

During it addition, manufacture said mixture, containing liquid (described reactant liquor or described lysate) by described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine being added to described polyamic acid, part can generate polyimides by chemical imidization.Therefore, when manufacturing said mixture, mitogenetic one-tenth polyimides and from the viewpoint of mixture evenly can be obtained in the middle part of mixture, liquid (described reactant liquor or described lysate) is contained preferably with respect to described polyamic acid, after adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, implement the operation of mixing (stirring) this mixture.Additionally, the operation of this mixing (stirring) more preferably carries out mixing the operation of (stirring) (under the temperature conditions of more preferably-30～60 DEG C, under the temperature conditions of particularly preferably 0 DEG C～40 DEG C) under the temperature conditions less than 80 DEG C.By implementing the operation of this mixing (stirring), can partly generate polyimides by the reaction of so-called chemical imidization and become uniform mixture.It addition, in the present invention, owing to being applied in combination described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, therefore, even if part generates polyimides and can also make the mixture that uniformity is the highest.Therefore, heat under the conditions of said temperature blended obtained by mixture when carrying out imidizate, it is intended to polyimides can be manufactured with relatively low-temperature heat, polyimides that light transmission the highest can be made more efficiently.At this, when temperature conditions during described mixing (stirring) is less than described lower limit, described mixture cannot be sufficiently carried out the reaction of part chemical imidization, thus need with high-temperature heating when tending to last imidizate, on the other hand, if it exceeds the described upper limit, then separate out the precipitation of polymer beyond required imidizate owing to having carried out, tending to described mixture and become uneven, result cannot obtain uniform thin film.

Additionally, as mentioned above relative to the reactant liquor containing described polyamic acid or the lysate containing described polyamic acid, in the case of mixing after adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, the time (carrying out the response time of chemical imidization reaction in described mixture) implementing this mixed processes is preferably 1 hour～50 hours, more preferably 12 hours～24 hours.When described incorporation time (response time) is less than described lower limit, tend to mixture is not sufficiently carried out chemical imidization reaction, need during final hot-imide to heat with high temperature, on the other hand, if it exceeds the described upper limit, then owing to excessively carrying out chemical imidization, thus tend to mixture and become uneven, and uniform thin film cannot be obtained.

Additionally, as atmospheric condition when mixing after adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, colour because of the oxygen air from preventing, from the viewpoint of preventing from being mixed into the steam in the air that can reduce molecular weight, the preferably inert gas conditions of nitrogen etc. or drying condition (such as mixing in drying baker).It addition, as pressure condition during manufacture mixture, be not particularly limited, preferably 0.01MPa～1MPa, more preferably 0.1MPa～0.3MPa.When described pressure is less than described lower limit, tend to solvent, described halogen carboxylic acid anhydrides or the gasification of described aliphatic category tertiary amine, on the other hand, if it exceeds the described upper limit, then the interpolation tending to converging operationJu Hecaozuo or described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine becomes difficulty.

So, as described mixture, it is preferably used and contains liquid (reactant liquor containing described polyamic acid or the lysate containing described polyamic acid) relative to described polyamic acid, after adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, under the temperature conditions less than 80 DEG C, mix (stirring) 1 hour～50 hours obtained mixture.Additionally, mixture after this stirring, as mentioned above, owing to part imidizate (chemical imidization) can be carried out in the mixture, therefore, polyimides containing the repetitive having represented by formula (2) described later and the polyamic acid represented by described formula (1).

(the imidizate operation of polyamic acid)

Then, the imidizate operation of polyamic acid is described.In the present invention, by the described mixture of use by described polyamic acid imidizate, thus the polyimides with the repetitive represented by following formula (2) is obtained.It addition, the R in following formula (2)¹And R²Each with the R in described formula (1)¹And R²Identical meanings (preferred situation is the most identical).

As the method for described imidizate, as long as using described mixture the method for described polyamic acid imidizate to be not particularly limited, known method being may be appropriately used, but preferably include to heat the operation of described mixture.Hot-imide can be carried out efficiently by this heating process.Additionally, as mixture used in this heating process, the reacted mixture of chemical imidization of described polyamic acid is carried out preferably by part in described mixture, from this viewpoint, more preferably utilize and contain liquid (reactant liquor containing described polyamic acid or the lysate containing described polyamic acid) relative to described polyamic acid, after adding described halogen carboxylic acid anhydrides and described aliphatic category tertiary amine, carry out mixing the mixture obtained by (stirring)；More preferably utilize and contain liquid relative to described polyamic acid and add described halogen carboxylic acid anhydrides and mix (stirring) under the temperature conditions less than 80 DEG C after described aliphatic category tertiary amine 1 hour～50 hours obtained mixture.I.e., in the present invention, the operation (operation of mixing (stirring) illustrated in the manufacture method of said mixture) of (mixing) described mixture is stirred and by described blend heated operation by the operation of described polyamic acid imidizate preferably includes.Thus, it is possible to after part carries out the chemical imidization reaction of described polyamic acid in described mixture, the heating of described mixture is carried out hot-imide, polyimides can be made more efficiently with the heating of more low temperature.

Additionally, described by blend heated operation, from the viewpoint of carrying out heating with more low temperature and preventing the coloring of polyimides, it is preferably with the operation of temperature (the more preferably temperature of low 100～200 DEG C than Tg, the more preferably temperature of low 120～180 DEG C than Tg) heating (burning till) the described mixture than low 80～300 DEG C of the glass transition temperature of obtained polyimides (Tg).If described heating-up temperature exceedes the described upper limit, then tend to the coloring being difficult to fully suppress polyimides, on the other hand, tend to during less than described lower limit cannot fully carry out imidizate.Additionally, by carrying out imidizate with the heating of described heating-up temperature, can heat with relatively low temperature, and can not observe in measuring at NMR the carboxylic acid (-COOH) from polyamic acid proton, from the way of the state of the proton of amide (NHCO) fully by polyamic acid imidizate.It addition, according to the present invention it is also possible to by with the low-temperature heat than low 80～300 DEG C of the glass transition temperature of polyimides (Tg), manufacturing the polyimides that flexibility is high.

It addition, " glass transition temperature (Tg) of polyimides " in the present invention can be tried to achieve by the assay method of following glass transition temperature (Tg).I.e., assay method as glass transition temperature (Tg), can use: form the polyimides of film shape, form long 20mm respectively, wide 5mm, after the thin film of the size of thick 0.02mm (20 μm), this film vacuum is dried (120 DEG C, 1 hour (Hr)), carry out after 1 hour (Hr) be thermally treated resulting in sample (dry film) with 200 DEG C under nitrogen atmosphere, use this sample, utilize thermo-mechanical analysis device (trade name " TMA8310 " that Rigaku manufactures) as determinator, use under nitrogen atmosphere and penetrate pattern, the condition that programming rate is 10 DEG C/min, the change of described sample at measuring 30 DEG C～400 DEG C and the method tried to achieve.

During it addition, heat described mixture by described polyamic acid imidizate, from the viewpoint of industrialization or reducing cost, preferably carry out heating (burning till) with more low temperature.From such a viewpoint, by described blend heated operation, heating-up temperature is preferably less than 300 DEG C, more preferably 80～250 DEG C, more preferably 100～230 DEG C, particularly preferably 100～210 DEG C.If described heating-up temperature exceedes the described upper limit, then tend to be difficult to owing to promoting heating-up temperature fully seek reducing or being difficult to the highest level suppression coloring of cost, on the other hand, less than during described lower limit reaction carry out slack-off, it is intended to be difficult to manufacture efficiently the polyimides of softness.It addition, the hot-imide of the heating even by such low temperature (such as less than 230 DEG C), owing to the present invention using described mixture, it is also possible to manufacture the polyimides of the mechanical property with abundant flexibility etc..

It addition, as implementing atmospheric condition during described blend heated operation, from the viewpoint of preventing from colouring because of the oxygen air or reducing molecular weight because of the steam in air, preferably under the inert gas atmosphere or vacuum of nitrogen etc..It addition, as implementing pressure condition during described blend heated operation, be not particularly limited, but preferably 0.01hPa～1MPa, more preferably 0.1hPa～0.3MPa.When described pressure is less than described lower limit, tend to solvent, described halogen carboxylic acid anhydrides or described aliphatic category tertiary amine transient evaporation and produce bubble or space, on the other hand, if it exceeds the described upper limit, then tend to be difficult to remove solvent, described halogen carboxylic acid anhydrides or described aliphatic category tertiary amine.

It addition, in the case of implementing by described blend heated operation, when described mixture contains solvent (such as, during for the mixture of solution shape), preferably enforcement dried before implementing heat treated.By described dried, it is also possible to after the polyamic acid of the repetitive having represented by above-mentioned formula (1) is made the form fractionation of film like etc., then implement heat treated.

As the temperature conditions of described dried, it is preferably-20～80 DEG C, more preferably 0～60 DEG C.When the temperature conditions of described dried is less than described lower limit, it is intended to cannot remove solvent when mixture contains solvent, on the other hand, if it exceeds the described upper limit, then the volatile ingredient boiling of solvent etc., it is intended to formed containing bubble or the thin film in space during masking.It addition, as the atmosphere in the method for described dried, preferably inert gas atmosphere (such as nitrogen atmosphere).It addition, from the viewpoint of being more effectively carried out being dried, as the pressure condition of described dried, preferably 0.01hPa～0.1MPa.In the case of Gai, such as in the case of manufacturing the polyimides of film like, can described mixture be coated on base material, implement described dried and heat treated such that it is able to manufacture the polyimides of film like with easy method.

Additionally, when manufacturing the polyimides of film like, as the base material for being coated with described mixture, it is not particularly limited, can be according to the shape etc. of the thin film being made up of the polyimides of target, suitably use the base material (such as, glass plate or metallic plate) being made up of the known material formed that can be used in thin film.

Additionally, coating process when mixture is coated base material as mentioned above is not particularly limited, known method (casting process etc.) be may be appropriately used, it is also possible to suitably use such as casting process, method of spin coating, spraying process, Dipcoat method, drip method, woodburytype, silk screen print method, toppan printing, die coating methods, curtain coating processes, ink jet printing method etc..

During it addition, coated on base material by mixture, as the coating thickness of this mixture, preferably making dried coating thickness is 1～200 μm, more preferably 5～100 μm.When the coating thickness of described mixture is less than described lower limit, it is intended to mechanical strength reduces, thin film dies down, on the other hand, if it exceeds the described upper limit this tend to be difficult to film forming processing.

Additionally, method as described imidizate, from the viewpoint of manufacturing efficiency, after being preferable to carry out obtaining the operation of described polyamic acid, it is directly used in organic solvent the reactant liquor obtained by making the tetracarboxylic dianhydride represented by above-mentioned formula (3) react (reactant liquor of the polyamic acid containing the repetitive having represented by above-mentioned formula (1)) (do not separate and there is the polyamic acid of the repetitive represented by above-mentioned formula (1) and use) with the aromatic diamine represented by above-mentioned formula (4), after obtaining mixture relative to the described reactant liquor described halogen carboxylic acid anhydrides of interpolation with described aliphatic category tertiary amine, after implementing dried removal solvent relative to this mixture, implement described heat treated (by described blend heated operation).It addition, obtain the operation of this mixture being implemented preferably as described above mix the operation of (stirring).

It addition, can be containing other repetitive beyond the repetitive represented by above-mentioned formula (2) by the polyimides obtained by the present invention.In the case of Gai, such as, in the operation obtaining described polyamic acid, it is possible to use the tetracarboxylic dianhydride represented by above-mentioned formula (3) and other tetracarboxylic dianhydride, these be made to react with described aromatic diamine.As other tetracarboxylic dianhydride beyond the tetracarboxylic dianhydride represented by described above-mentioned formula (3), can suitably use known tetracarboxylic dianhydride.nullSuch as，Pyromellitic acid dianhydride can be enumerated、3,3’,4,4 '-benzophenone tetracarboxylic dianhydride、3,3’,4,4 '-biphenyl sulfone tetracarboxylic dianhydride、1,4,5,8-naphthalene tetracarboxylic acid dianhydride、2,3,6,7-naphthalene tetracarboxylic acid dianhydride、3,3’,4,4 '-Biphenyl Ether tetracarboxylic dianhydride、3,3’,4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride、3,3’,4,4 '-tetraphenyl silane tetracarboxylic dianhydride、1,2,3,4-furan tetracarboxylic dianhydride、4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride、4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide. dianhydride、4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride、3,3’,4,4 '-perfluor isopropylidene two phthalandione dianhydride、4,4’-(2,2-hexafluoroisopropylidenyl) two phthalandione dianhydrides、3,3’,4,4 '-biphenyl tetracarboxylic dianhydride、2,3,3’,4 '-biphenyl tetracarboxylic dianhydride、Double (phthalandione) phenyl phosphine oxide dianhydride、To phenylene-bis-(triphenyl phthalandione) dianhydride、Metaphenylene-bis-(triphenyl phthalandione) dianhydride、Double (triphenyl phthalandiones)-4,4 '-diphenyl ether dianhydride、Double (triphenyl phthalandiones)-4,Aromatic tetracarboxylic acid's dianhydride etc. of 4 '-diphenyl methane dianhydride etc..During it addition, use described aromatic tetracarboxylic acid, in order to prevent colouring because of CT, its usage amount preferably suitably changes in the scope that obtained polyimides can be made to have the sufficiently transparency.

[polyimides]

As described polyimides, preferred glass transition temperature (Tg) is more than 250 DEG C, more preferably 300～500 DEG C.Tend to be difficult to reach sufficient thermostability, on the other hand, if it exceeds the described upper limit is then tended to be difficult to manufacture the polyimides having characteristics that when described glass transition temperature (Tg) is less than described lower limit.The glass transition temperature (Tg) of described polyimides can use the assay method of above-mentioned glass transition temperature (Tg) to try to achieve.

Further, as the number-average molecular weight (Mn) of described polyimides, it is preferably 1000～1000000 with polystyrene conversion, more preferably 10000～100000.Tend to be difficult to reach sufficient thermostability, on the other hand, if it exceeds the described upper limit is then tended to be difficult to when described number-average molecular weight is less than described lower limit.

It addition, as the weight average molecular weight (Mw) of described polyimides, it is preferably 1000～5000000 with polystyrene conversion.It addition, the lower limit of the numerical range as described weight average molecular weight (Mw), more preferably 1000, more preferably 5000, particularly preferably 10000.It addition, the higher limit of the numerical range as weight average molecular weight (Mw), more preferably 5000000, more preferably 500000, particularly preferably 50000.Tend to be difficult to reach sufficient thermostability, on the other hand, if it exceeds the described upper limit is then tended to be difficult to when described weight average molecular weight is less than described lower limit.

Further, the molecular weight distribution (Mw/Mn) of described polyimides is preferably 1.1～5.0, more preferably 1.5～3.0.Tend to be difficult to manufacture, on the other hand, if it exceeds the described upper limit is then tended to be difficult to obtain uniform thin film when this molecular weight distribution is less than described lower limit.Additionally, the molecular weight (Mw or Mn) of described polyimides and molecular weight distribution (Mw/Mn) can be by using chromatograph of gel permeation (GPC, TosohCorporation manufactures, trade name: HLC-8020/ post 4: TosohCorporation manufactures, trade name: TSKgelGMH_HRDeng) as determinator, use oxolane (THF), chloroform, DMF (DMF) etc. to be measured as solvent, the data recorded by polystyrene conversion are tried to achieve.

It addition, the linear expansion coefficient of described polyimides is preferably-10～100ppm/ DEG C (more preferably 0～80ppm/ DEG C).When described linear expansion coefficient is less than described lower limit, tend to be deformed when other materials such as the inorganic substances with metal, metal-oxide or glass etc. carry out Composite, on the other hand, if it exceeds the described upper limit then when less than lower limit in the same manner as tend to be deformed when carrying out Composite with other materials such as inorganic substances such as metal, metal-oxide or glass.

The linear expansion coefficient of described polyimides can use: uses the sample of the size of long 20mm, wide 5mm, thick 0.02mm (20 μm), utilize thermo-mechanical analysis device (trade name " TMA8310 " that Rigaku manufactures) as determinator, use stretch mode (49mN) in a nitrogen atmosphere, the condition of programming rate 5 DEG C/min measures the change of longitudinal length of described sample at 50 DEG C～200 DEG C, tries to achieve the thus obtained value of meansigma methods of the length change of within the temperature range of 100 DEG C～200 DEG C every 1 DEG C.It addition, the glass transition temperature of described polyimides and linear expansion coefficient can be by suitably changing the R in described formula (2)¹～R²Kind etc. or become the value in described numerical range containing the repetitive represented by multiple (more than two kinds) described formula (2).

It addition, described polyimides preferably clear is high, further preferred 400～the mean transmissivity of light of 800nm wavelength region be more than 80% (more preferably more than 85%, particularly preferably more than 87%).Described mean transmissivity can be reached fully by heating-up temperature when manufacturing is set as more low temperature.It addition, as described transmitance, the value that the trade name " UV, visible light near infrared spectrometer V-570 " using Japan's light splitting to manufacture records can be used as determinator.

It addition, as described polyimides, heat decomposition temperature (Td) is preferably more than 450 DEG C, more preferably 480～600 DEG C.Tend to be difficult to reach sufficient thermostability, on the other hand, if it exceeds the described upper limit is then tended to be difficult to manufacture the polyimides having characteristics that when described heat decomposition temperature (Td) is less than described lower limit.Additionally, described heat decomposition temperature (Td) can be by using TG/DTA220 Thermgravimetric Analysis Apparatus (SIINanoTechnologyInc. manufacture), and in nitrogen stream, (200mL/min) measures the temperature of the intersection point of the line extended on the decomposition curve before and after thermal decomposition and try to achieve with the condition of 10 DEG C/min of programming rate.

As described polyimides, weight reduces by the temperature of 5% and is preferably more than 400 DEG C, more preferably 450～550 DEG C.Described weight tends to be difficult to reach sufficient thermostability, on the other hand, if it exceeds the described upper limit is then tended to be difficult to manufacture the polyimides having characteristics that when reducing by the temperature of 5% less than described lower limit.By flowing into nitrogen in a nitrogen atmosphere and can begin to warm up from room temperature (25 DEG C) lentamente it addition, described weight reduces by the temperature of 5%, the weight of the sample used by mensuration reduces by the temperature of 5% and tries to achieve.It addition, as this sample, preferably prepare the thin film use of 5 length of a film 2mm, wide 2mm, thick 20 μm.

As it has been described above, obtained by the polyimides of the present invention is due to the manufacture method of the polyimides for using the invention described above, therefore, it can prevent coloring fully, there is abundant high-caliber light transmission and the highest thermostability.It addition, obtained by the manufacture method that the polyimides of the present invention is the polyimides using the invention described above, therefore, there is sufficient flexibility.Therefore, the polyimides of the present invention is suitable for the resin raw material etc. used by the replacement of glass, such as, is suitable for being manufactured as the material etc. of the substrate being made up of transparent resin material used by the substrate of the mobile device of smart mobile phone or tablet device etc..

Embodiment

Further illustrate the present invention below based on embodiment and comparative example, but the present invention is not limited to below example.

First, the appraisal procedure of the characteristic of the compound obtained in each synthesis example, each embodiment, each comparative example or thin film etc. is illustrated.

The qualification ＞ of ＜ molecular structure

The qualification of the molecular structure of the compound obtained in each embodiment etc. can (Japan Spectroscopy Corporation manufactures, FT/IR-460, FT/IR-4100 by using infrared spectroscopic analysis device；ThermoFisherScientificK.K. manufacture, and NMR measuring machine (VARIAN company manufactures, the JNM-Lambda500 that trade name: UNITYINOVA-600 and Jeol Ltd. manufacture) measures IR and NMR spectra is carried out NICOLET380FT-IR).

Mensuration ＞ of ＜ glass transition temperature (Tg)

Glass transition temperature (Tg) is by being formed long 20mm respectively by the polyimides (polyimides of film shape) obtained in each embodiment and each comparative example, wide 5mm, after the thin film of the size of thick 0.02mm (20 μm), this film vacuum is dried (120 DEG C, 1 hour (Hr)), at 200 DEG C, heat treatment 1 hour (Hr) obtains sample under nitrogen atmosphere, use this sample obtained (dry film) respectively, utilize thermo-mechanical analysis device (trade name " TMA8310 " that Rigaku manufactures) as determinator, use under nitrogen atmosphere and penetrate pattern, the condition that programming rate is 10 DEG C/min, the change of described sample at measuring 30 DEG C～400 DEG C and obtain.

＜ weight reduces mensuration ＞ of the temperature of 5%

The weight of the polyimides obtained in embodiment and comparative example reduces by the temperature of 5% by 5 length of a film 2mm, wide 2mm, the sample of film shape of thick 20 μm being respectively put in aluminum sample dish, use TG/DTA7200 Thermgravimetric Analysis Apparatus (SIINanoTechnologyInc. manufacture) as determinator, the nitrogen that circulates is while being heated the scopes of 600 DEG C by room temperature (25 DEG C) with the condition of 10 DEG C/min, and the weight measuring the sample used reduces by the temperature of 5% and tries to achieve.

Mensuration ＞ of ＜ intrinsic viscosity [η]

When embodiment and comparative example manufacture thin film etc., the automatic viscosity determinator (trade name " VMC-252 ") that the intrinsic viscosity [η] of the polyamic acid obtained as intermediate manufactures by using clutch company, with N, N-dimethyl acetylamide is as solvent, after modulation concentration is the mensuration sample of polyamic acid of 0.5g/dL, record under the temperature conditions of 30 DEG C.

Mensuration ＞ of ＜ linear expansion coefficient (CTE)

nullLinear expansion coefficient is by being formed long 20mm respectively by the polyimides (polyimides of film shape) obtained in each embodiment and each comparative example、Wide 5mm、After the thin film of the size of thick 0.02mm (20 μm)，This film vacuum is dried (120 DEG C，1 hour (Hr))，At 200 DEG C, heat treatment 1 hour (Hr) obtains sample (dry film) in a nitrogen atmosphere，Use this sample respectively，Utilize thermo-mechanical analysis device (trade name " TMA8310 " that Rigaku manufactures) as determinator，Use stretch mode (49mN) in a nitrogen atmosphere、The length change of described sample at the condition mensuration 50 DEG C～200 DEG C that programming rate is 5 DEG C/min，The meansigma methods of the length change trying to achieve within the temperature range of 100 DEG C～200 DEG C every 1 DEG C is measured.

Mensuration ＞ of the mean transmissivity of the light of the wavelength region of ＜ 400～800nm

After the trade name " UV, visible light near infrared spectrometer V-570 " that the mean transmissivity of the light of the wavelength region of the 400～800nm of the polyimides (polyimides of film shape) obtained in each embodiment and each comparative example manufactures by using Japan's light splitting measures transmitance as determinator, the meansigma methods of the transmitance trying to achieve the light of the wavelength region of 400～800nm is measured.

The pliability of ＜ thin film and mensuration ＞ of intensity

For the pliability of polyimides (polyimides of film shape) obtained in each embodiment and each comparative example and intensity (mechanical strength), after the thin film of the size forming long 50mm, wide 10mm, thick 0.02mm (20 μm) respectively, repeat to be wound in commercially available round pencil ([diameter]: 8mm) 10 times (round pencil flexing test) time, thin film is judged as flexible (soft) thin film (intensity: fully with abundant intensity in the case of not splitting, pliability: fully), on the contrary, the most film-forming situation or i.e. allow to form thin film but in round pencil flexing test, thin film produces in the case of crack and is judged as not having flexual thin film, it is crisp (fragility) thin film (intensity: crisp, pliability: not enough).

(embodiment 1)

The modulation ＞ of ＜ polyamic acid

By 3,4 '-diamino-diphenyl ether (0.40052g, 2.000mmol, it is referred to as " 3; 4 '-DDE " below according to situation) and N, N-dimethyl acetylamide (2.00g is referred to as " DMAc " below according to situation) adds in there-necked flask, under nitrogen flowing in temperature: 20 DEG C, use mechanical agitator stirring to obtain lysate in about 10 minutes under conditions of pressure 0.1MPa.Then, funnel is used to import to have been introduced in the described there-necked flask of described lysate by the tetracarboxylic dianhydride 0.76879g (2.00mmol is referred to as " acid dianhydride (A) " below according to situation) represented by following formula (6).It addition, the described tetracarboxylic dianhydride being attached in funnel flows into DMAc (2.00g), whole amount (0.76879g) is imported in described lysate.

Then, in nitrogen atmosphere, temperature: 20 DEG C, under conditions of pressure 0.1MPa, use mechanical agitator with the continuously stirred described lysate being imported with described tetracarboxylic dianhydride of the mixing speed of 30rpm 17 hours, make described tetracarboxylic dianhydride and 3,4 '-DDE reactions generate polyamic acid, obtain the reactant liquor containing polyamic acid.It addition, obtained polyamic acid is for having the polyamic acid of the repetitive represented by formula (1), the R in described repetitive, in formula (1)¹For the group represented by above-mentioned formula (I-9), and R²For the group represented by following formula (II-4-1) or (II-4-2).

It addition, for the viscosity measuring thus obtained polyamic acid, the liquid (liquid of the amount of the sampling polyamic acid containing 0.25g) of sampling part from described reactant liquor, with the polyamic acid solution of DMAc dilution modulation 0.5g/dL.Then, the assay method using described intrinsic viscosity [η] tries to achieve intrinsic viscosity [η].I.e., use the polyamic acid solution thus modulated, and (the automatic viscosity determinator (trade name " VMC-252 ") that clutch company manufactures measures the viscosity (must dense log viscosities) of polyamic acid solution to use Ostwald viscosimeter in the temperature chamber of 30 DEG C.Its result, the intrinsic viscosity [η] of obtained polyamic acid is 0.46dL/g.

The modulation ＞ of ＜ mixture

Then, while the reactant liquor 2.9g (mole (total amount of the described repetitive in described reactant liquor) of the repetitive of polyamic acid: the 1.0mmol containing polyamic acid that will obtain in the modulating process of described polyamic acid with ice bath, about half amount of described reactant liquor) cooling, triethylamine 139 μ L (1.0mmol) is joined in described reactant liquor.By adding this triethylamine thus the viscosity of described reactant liquor rises, part nebulousurine, it is therefore contemplated that generate the amine salt of polyamic acid in described reactant liquor quickly.Then, the described reactant liquor after adding relative to described triethylamine, add trifluoroacetic anhydride 86 μ L (0.6mmol).It addition, described reactant liquor about 20 minutes viscosity after adding trifluoroacetic anhydride reduces, form uniform and transparent yellow solution (mixture).Then, in nitrogen atmosphere, temperature: 20 DEG C, stir with the mixing speed of 30rpm under conditions of pressure 0.1MPa obtained by yellow solution 12 hours.So obtain the mixture containing described polyamic acid, triethylamine and trifluoroacetic anhydride.

It addition, for the structure confirming the composition in the mixture after this stirring, take out the mixture obtained by after part stirring, be allowed to after reprecipitation obtains white solid in methanol, be dried and a portion is dissolved in DMSO-d₆Middle modulation NMR sample.Then, use described drying sample and NMR sample, utilize above-mentioned molecular structure qualification the method described in method measure IR and¹H-NMR spectrum.In obtained result, by shown in Figure 1 for the IR spectrum of the composition (described reprecipitation thing) in described mixture, by the composition (described reprecipitation thing) in described mixture¹H-NMR spectrum is shown in Figure 2, shown in Fig. 2¹Enlarged drawing near 6ppm～13ppm of H-NMR spectrum is shown in Figure 3.According to these measurement results (result shown in Fig. 1～Fig. 3), the proton (near 12ppm) of the carboxylic acid (-COOH) from polyamic acid can be observed and from the proton (near 10ppm) of amide (NHCO), confirm that closed loop rate is 32% according to the integrated intensity of polyamic acid.From this result, the polyamic acid part imidizate in described mixture.It addition, polyimides does not separates out in described mixture, form full and uniform solution.

The modulation ＞ of ＜ polyimides

Then, mixture 0.6mL obtained by modulating process by described mixture is passed through cast coat (using casting process to be coated with) on glass baseplate surface (long 75mm, wide 25mm), then, under the pressure of 1hPa, stand 2 hours with the temperature conditionss of 80 DEG C and thus remove solvent (DMAc), it is allowed to dry, obtains the dry coating (thick 20 μm) of described mixture.Then, by the dry coating of described mixture heat treated 1 hour under pressure 1hPa, nitrogen atmosphere, the temperature conditions of 200 DEG C, thin film is obtained.It addition, obtained thin film is the flexible transparent membrane with sufficient intensity (mechanical strength).

In order to identify the structure of the composition forming thus obtained thin film, after making the Film Fractionation obtained by a part form NMR sample in deuterochloroform, use the film like sample (IR sample) after being taken out by a part of above-mentioned thin film and the NMR sample that obtains as mentioned above, utilize the method mensuration IR described in the authentication method of above-mentioned molecular structure and¹H-NMR spectrum.In the result obtained, by shown in Figure 4 for the IR spectrum of the constituent of described thin film, by the constituent of described thin film¹H-NMR spectrum is shown in Figure 5, shown in Fig. 5¹Enlarged drawing near the 6ppm of H-NMR spectrum～near 13ppm is shown in Figure 6.According to these measurement results (result shown in Fig. 4～Fig. 6), if mensuration closed loop rate, then due to entirely without observing the proton (near 12ppm) of the carboxylic acid (-COOH) from amic acid or from the proton (near 10ppm) of amide (NHCO), therefore, it is known that imidizate completely.According to this result, obtained thin film by have represented by described formula (2) repetitive (in formula (2), R¹For the group represented by above-mentioned formula (I-9), and R²Group for represented by following formula (II-4-1) or (II-4-2)) polyimides constitute.

It addition, use the assay method of above-mentioned glass transition temperature (Tg) to measure the glass transition temperature of thus obtained polyimides (thin film), the Tg of the polyimides (thin film) obtained by result is 333 DEG C.It addition, the linear expansion coefficient of polyimides (thin film) obtained by using the assay method of above-mentioned linear expansion coefficient (CTE) to measure, the CTE of the polyimides (thin film) obtained by result is 56ppm/K.It addition, try to achieve mean transmissivity and the temperature of weight minimizing 5% by said determination method, obtained by result, the mean transmissivity of the light of 400～800nm wavelength region of polyimides (thin film) is 88%, and it is 488 DEG C that weight reduces by the temperature of 5%.

(embodiment 2)

The modulation ＞ of ＜ polyamic acid

Method as the method for " modulation of polyamic acid " that use and use in embodiment 1, obtains the reactant liquor containing polyamic acid.

The modulation ＞ of ＜ mixture

Then, reactant liquor 2.9g (the mole of the repetitive of polyamic acid: the 1.0mmol containing polyamic acid obtained in the modulating process of described polyamic acid while being cooled with an ice bath, about half amount of described reactant liquor), while after being sequentially added into triethylamine 278 μ L (2.0mmol) and trifluoroacetic anhydride 287 μ L (2.0mmol), in nitrogen atmosphere, temperature: 20 DEG C, mixing speed with 30rpm stirs 23 hours under conditions of pressure 0.1MPa, obtains the mixture containing described polyamic acid, triethylamine and trifluoroacetic anhydride.It addition, the result of this stirring, obtained mixture is uniform and transparent yellow solution.

It addition, the structure of the composition in order to confirm after stirring in mixture, measure similarly to Example 1 IR and¹H-NMR spectrum.In the result obtained, by shown in Figure 7 for the IR spectrum of the composition (described reprecipitation thing) in described mixture, by the composition (described reprecipitation thing) in described mixture¹H-NMR spectrum is shown in Figure 8, shown in Fig. 8¹Enlarged drawing near the 6ppm of H-NMR spectrum～near 13ppm is shown in Figure 9.According to these measurement results (result shown in Fig. 8～Fig. 9), described reprecipitation thing observes the proton (near 12ppm) of the carboxylic acid (-COOH) from polyamic acid and from the proton (near 10ppm) of amide (NHCO), confirmed that by integrated intensity the closed loop rate of polyamic acid is 40%.From this result, the polyamic acid part imidizate in described mixture.It addition, polyimides does not separates out in described mixture, for full and uniform liquid.

The modulation ＞ of ＜ polyimides

Then, in addition to using, as described mixture, the mixture obtained in the modulating process of said mixture, use the method identical with the method for " modulation of polyimides " that use in embodiment 1, obtain polyimides (thin film).It addition, obtained thin film is the flexible transparent membrane with sufficient intensity (mechanical strength).

In order to identify the structure of composition forming this thin film, measure similarly to Example 1 IR and¹H-NMR spectrum.In the result obtained, by shown in Figure 10 for the IR spectrum of the constituent of described thin film, by the constituent of described thin film¹H-NMR spectrum is shown in Figure 11, shown in Figure 11¹Enlarged drawing near the 6ppm of H-NMR spectrum～near 13ppm is shown in Figure 12.According to this measurement result (result shown in Figure 10～Figure 12), if mensuration closed loop rate, then due to entirely without observing the proton (near 12ppm) of the carboxylic acid (-COOH) from amic acid or from the proton (near 10ppm) of amide (NHCO), therefore, it is known that imidizate completely.From this result, obtained thin film by have represented by described formula (2) repetitive (in formula (2), R¹For the group represented by above-mentioned formula (I-9), and R²Group for represented by following formula (II-4-1) or (II-4-2)) polyimides constitute.

Additionally, try to achieve the glass transition temperature (Tg) of obtained polyimides (thin film), linear expansion coefficient (CTE), 400～the mean transmissivity of light of 800nm wavelength region, the temperature of weight minimizing 5% similarly to Example 1, result Tg is 333 DEG C, CTE is 57ppm/K, described mean transmissivity is 88%, and it is 484 DEG C that weight reduces by the temperature of 5%.

(embodiment 3)

The modulation ＞ of ＜ polyamic acid

Except using 4,4 '-diamino-diphenyl ether (4,4 '-DDE, 0.40053g, 2.000mmol) replace 3,4 '-diamino-diphenyl ether (0.40052g, 2.000mmol), the usage amount of acid dianhydride (A) is changed to beyond 0.76878g (2.00mmol) by 0.76879g (2.00mmol), uses the method identical with the method for " modulation of polyamic acid " that use in embodiment 1, obtain the reactant liquor containing polyamic acid.

It addition, the polyamic acid obtained is for having the polyamic acid of the repetitive represented by described formula (1), this repetitive is the R in formula (1)¹Group represented by above-mentioned formula (I-9) and R²For the group represented by following formula (II-4-3).It addition, use the assay method of described intrinsic viscosity [η], trying to achieve the intrinsic viscosity [η] of obtained polyamic acid similarly to Example 1, fruiting characteristic viscosity [η] is 0.87dL/g.

The modulation ＞ of ＜ mixture

Then, in addition to using the thus obtained reactant liquor containing polyamic acid, use the method identical with the method for " modulation of mixture " that use in embodiment 1, obtain mixture.It addition, the structure of the composition measured similarly to Example 1 in the mixture after stirring, result¹Observing the proton of the carboxylic acid (-COOH) from amic acid in H-NMR spectrum and from the proton of amide (NHCO), the closed loop rate being identified through the polyamic acid that integrated intensity is tried to achieve is 40%.From this result, the polyamic acid part imidizate in described mixture.It addition, polyimides does not separates out in described mixture, for full and uniform solution.

The modulation ＞ of ＜ polyimides

In order to identify the structure of composition forming this thin film, measure similarly to Example 1 IR and¹H-NMR spectrum.Based on this IR and¹The measurement result of H-NMR spectrum, if the closed loop rate of the polyamic acid in the thin film obtained by Ce Dinging, then owing to not observing the proton of the carboxylic acid (-COOH) from amic acid completely or from the proton of amide (NHCO), therefore, complete imidizate.From this result, obtained thin film by have represented by described formula (2) repetitive (in formula (2), R¹For the group represented by above-mentioned formula (I-9), and R²Group for represented by above-mentioned formula (II-4-3)) polyimides constitute.

Additionally, try to achieve the mean transmissivity of light of wavelength region of the glass transition temperature (Tg) of obtained polyimides (thin film), linear expansion coefficient (CTE), 400～800nm, the temperature of weight minimizing 5% similarly to Example 1, result Tg is 354 DEG C, CTE is 49ppm/K, described mean transmissivity is 87%, and it is 468 DEG C that weight reduces by the temperature of 5%.

(embodiment 4)

The modulation ＞ of ＜ polyamic acid

By 4,4 '-diaminobenzene formailide (0.45452g, 2.000mmol, be referred to as " 4; 4 '-DABA " below according to situation) and DMAc (2.00g) join in there-necked flask, under nitrogen flowing with temperature: 20 DEG C, the condition use mechanical agitator stirring about 10 minutes of pressure 0.1MPa, obtain lysate.Then, funnel is used to be imported by the tetracarboxylic dianhydride 0.76878g (2.00mmol: acid dianhydride (A)) represented by above-mentioned formula (6) in the described there-necked flask being imported with described lysate.It addition, flow into the described tetracarboxylic dianhydride being attached in funnel with DMAc (2.90g), whole amount (0.76878g) is imported in described lysate.

Then, in nitrogen atmosphere, temperature: 20 DEG C, use under conditions of pressure 0.1MPa mechanical agitator with the continuously stirred described lysate being imported with described tetracarboxylic dianhydride of the mixing speed of 30rpm 18 hours, make described tetracarboxylic dianhydride and 4,4 '-DABA reactions generate polyamic acid, obtain the reactant liquor containing polyamic acid.It addition, obtained polyamic acid is for having the polyamic acid of the repetitive represented by formula (1), this repetitive is the R in formula (1)¹Group represented by above-mentioned formula (I-9) and R²For the group represented by following formula (II-4-4).It addition, use the assay method of described intrinsic viscosity [η], trying to achieve the intrinsic viscosity [η] of obtained polyamic acid similarly to Example 1, fruiting characteristic viscosity [η] is 0.77dL/g.

The modulation ＞ of ＜ mixture

Then, reactant liquor 3.1g (the amount of polyamic acid repetitive: the 1.0mmol containing polyamic acid obtained in the modulating process of described polyamic acid is diluted with the DMAc of 6.0g, about half amount of described reactant liquor), then, it is cooled with an ice bath and triethylamine 139 μ L (1.0mmol) is added in described reactant liquor.By adding this triethylamine thus the viscosity of described reactant liquor rises quickly, generating partial gel shape thing, but stir about 3 hours with the temperature conditions of 20 DEG C, result obtains uniform solution.Then, described solution is cooled down while trifluoroacetic anhydride 86 μ L (0.6mmol) being added in described solution with ice bath.It addition, described solution about about 20 minutes viscosity after trifluoroacetic anhydride adds reduces, obtain uniform and transparent solution.Then, in nitrogen atmosphere, temperature: 20 DEG C, stir with the mixing speed of 30rpm under conditions of pressure 0.1MPa obtained by clear solution 12 hours.Thus obtain the mixture containing described polyamic acid, triethylamine and trifluoroacetic anhydride.

It addition, the structure of the composition measured similarly to Example 1 in the mixture after stirring, result¹Observing the proton of the carboxylic acid (-COOH) from amic acid in H-NMR spectrum and from the proton of amide (NHCO), the closed loop rate of the polyamic acid tried to achieve by integrated intensity confirms as 40%.From this result, the polyamic acid part imidizate in described mixture.It addition, polyimides does not separates out in described mixture, for full and uniform solution.

The modulation ＞ of ＜ polyimides

In order to identify the structure of composition forming this thin film, measure similarly to Example 1 IR and¹H-NMR spectrum.Based on this IR and¹The measurement result of H-NMR spectrum, if the closed loop rate of the polyamic acid in the thin film obtained by Ce Dinging, owing to not observing the proton of the carboxylic acid (-COOH) from amic acid completely or from the proton of amide (NHCO), it is thus identified that be complete imidizate.From this result, obtained thin film by have represented by described formula (2) repetitive (in formula (2), R¹Group represented by above-mentioned formula (I-9) and R²For the group represented by above-mentioned formula (II-4-4).) polyimides constitute.

Additionally, try to achieve the glass transition temperature (Tg) of obtained polyimides (thin film), linear expansion coefficient (CTE), 400～the mean transmissivity of light of 800nm wavelength region, the temperature of weight minimizing 5% similarly to Example 1, result Tg is more than 400 DEG C, CTE is 15ppm/K, described mean transmissivity is 87%, and it is 481 DEG C that weight reduces by the temperature of 5%.

(comparative example 1)

Except the modulating process of mixture is not carried out, the reactant liquor containing the polyamic acid described reactant liquor of triethylamine and trifluoroacetic anhydride (use be not added with) obtained in the modulating process of described polyamic acid is used to replace described mixture in the modulating process of polyimides, and temperature conditions during the heat treated of dry coating in the modulating process of polyimides is changed to beyond 300 DEG C by 200 DEG C, modulate polyimides (thin film) similarly to Example 1.But, it is impossible to obtain pliability thin film, obtained thin film crisp (fragility).

(comparative example 2)

In addition to temperature conditions when by the heat treated of dry coating is changed to 350 DEG C by 300 DEG C, obtain polyimides (thin film) in the same manner as comparative example 1.Obtained thin film is flexible transparent membrane.Additionally, try to achieve the glass transition temperature (Tg) of obtained polyimides (thin film), linear expansion coefficient (CTE), 400～the mean transmissivity of light of 800nm wavelength region, the temperature of weight minimizing 5% similarly to Example 1, result Tg is 333 DEG C, CTE is 57ppm/K, described mean transmissivity is 84%, and it is 484 DEG C that weight reduces by the temperature of 5%.

(comparative example 3)

The modulation ＞ of ＜ polyamic acid

Employing and the method that in embodiment 1, the method for " modulation of polyamic acid " of employing is identical, obtain the reactant liquor containing polyamic acid.

The modulation ＞ of ＜ mixture

Then, except using the reactant liquor (mole of the repetitive of polyamic acid: the 1.0mmol containing polyamic acid obtained in the modulating process of the described polyamic acid of 2.9g, about half amount of described reactant liquor), and in described reactant liquor, add pyridine 81 μ L (1.0mmol) replace beyond triethylamine 139 μ L (1.0mmol), employing and the method that in embodiment 1, the method for " modulation of mixture " of employing is identical, obtain containing polyamic acid 2.9g (amount of repetitive is 1.0mmol), pyridine 81 μ L (1.0mmol) and the mixture of trifluoroacetic anhydride 86 μ L (0.6mmol).

The modulation ＞ of ＜ polyimides

Then, in addition to using, as described mixture, the mixture obtained in the modulating process of said mixture, employing and the method (heating-up temperature: 200 DEG C) that in embodiment 1, the method for " modulation of polyimides " of employing is identical, modulation polyimides (thin film).But, it is impossible to obtain flexible thin film, obtained thin film crisp (fragility).

(comparative example 4)

Except in the modulating process of polyimides, the temperature conditions during heat treated of dry coating is changed to beyond 350 DEG C by 200 DEG C, modulates polyimides (thin film) in the same manner as comparative example 3.But, it is impossible to obtain flexible thin film, obtained thin film crisp (fragility).

(comparative example 5)

The modulation ＞ of ＜ polyamic acid

The modulation ＞ of ＜ mixture

Then, except using the reactant liquor 2.9g (mole of the repetitive of polyamic acid: the 1.0mmol containing polyamic acid obtained in the modulating process of described polyamic acid, about half amount of described reactant liquor), and in reactant liquor, add acetic anhydride 57 μ L (0.6mmol) replace beyond trifluoroacetic anhydride 86 μ L (0.6mmol), employing and the method that in embodiment 1, the method for " modulation of mixture " of employing is identical, obtain containing polyamic acid 2.9g (amount of repetitive is 1.0mmol), triethylamine 139 μ L (1.0mmol) and the mixture of acetic anhydride 57 μ L (0.6mmol).

The modulation ＞ of ＜ polyimides

(comparative example 6)

Except in the modulating process of polyimides, the temperature conditions during heat treated of dry coating is changed to beyond 300 DEG C by 200 DEG C, modulates polyimides (thin film) in the same manner as comparative example 5.But, it is impossible to obtain flexible thin film, obtained thin film crisp (fragility).

(comparative example 7)

Except in the modulating process of polyimides, the temperature conditions during heat treated of dry coating is changed to beyond 350 DEG C by 200 DEG C, modulates polyimides (thin film) in the same manner as comparative example 5.Obtained thin film is flexible transparent membrane.Additionally, try to achieve the glass transition temperature (Tg) of obtained polyimides (thin film), linear expansion coefficient (CTE), 400～the mean transmissivity of light of 800nm wavelength region, the temperature of weight minimizing 5% similarly to Example 1, result Tg is 333 DEG C, CTE is 57ppm/K, described mean transmissivity is 85%, and it is 484 DEG C that weight reduces by the temperature of 5%.

(comparative example 8)

The modulation ＞ of ＜ polyamic acid

The modulation ＞ of ＜ mixture

Then, except using the reactant liquor 2.9g (amount of polyamic acid repetitive: the 1.0mmol containing polyamic acid obtained in the modulating process of described polyamic acid, about half amount of described reactant liquor), in described reactant liquor, add pyridine 81 μ L (1.0mmol) replace triethylamine 139 μ L (1.0mmol), in described reactant liquor, add acetic anhydride 57 μ L (0.6mmol) further replace beyond trifluoroacetic anhydride 86 μ L (0.6mmol), employing and the method that in embodiment 1, the method for " modulation of mixture " of employing is identical, obtain containing polyamic acid 2.9g (1.0mmol), pyridine 81 μ L (1.0mmol) and the mixture of acetic anhydride 57 μ L (0.6mmol).But, obtained mixture is uneven, and generating in this mixture has the gel insoluble in DMAc, therefore, it is impossible to casting on the glass substrate, it is impossible to form thin film.

Below, relevant each embodiment and each comparative example, starting compound etc. used in the modulation of polyamic acid (polyamicacid) is shown in Table 1, characteristic and the modulation condition of the mixture of modulation in each embodiment and each comparative example are shown in Table 2, the characteristic of the polyimides of modulation in each embodiment and each comparative example is shown in Table 3.

[table 1]

[table 2]

[table 3]

For the mark (*) in table, polyimides owing to obtaining in comparative example 1,3～6 does not measure Tg, therefore, the value of relevant with these comparative examples " heating-up temperature and the difference (absolute value) of the Tg of polyimides " represents the value utilizing the value (333 DEG C) of the Tg using the polyimides obtained in the embodiment 1 of the monomer identical with these comparative examples to calculate.

Be can confirm that by the result shown in table 1～3, when being applied in combination halogen carboxylic acid anhydrides (trifluoroacetic anhydride) and aliphatic category tertiary amine (triethylamine) as acid imide agent, i.e., when using the mixture containing described polyamic acid, halogen carboxylic acid anhydrides (trifluoroacetic anhydride) and aliphatic category tertiary amine (triethylamine) (embodiment 1～4), although heating (burning till) this mixture at a temperature of 200 DEG C substantially low, it is also possible to manufacture the flexible polyimides with sufficient intensity (mechanical strength).Additionally, when using the described mixture containing polyamic acid, halogen carboxylic acid anhydrides and aliphatic category tertiary amine (embodiment 1～4), the mean transmissivity of obtained polyimides (thin film) is more than 87%, confirm fully suppress coloring when manufacturing, and the Tg of obtained polyimides (thin film) is more than 330 DEG C, having further confirmed that weight reduces by the temperature of 5% is more than 460 DEG C, has the highest thermostability.From these results, the present invention (embodiment 1～4) utilizes the chemical imidization method using acid imide agent, with the abundant low-temperature heat of 200 DEG C, can manufacture efficiently and there is abundant flexibility, the highest light transmission and the polyimides of the highest thermostability.

In contrast, do not use any acid imide agent, when heating attempt hot-imide with the temperature conditions of 300 DEG C (temperature lower than Tg) (comparative example 1), obtained polyimides is more crisp, and intensity is not enough, it is impossible to as thin film.It addition, the present invention infers that when the above results is due to only with 300 DEG C of hot acyl Asias, hot-imide temperature is lower than glass transition temperature, thus, it is impossible to start the strand of polyamic acid, thus the lifting of molecular weight and the lifting of acid imide rate cannot be reached.Additionally, do not use any acid imide agent, when heating attempt hot-imide with the temperature conditions of 350 DEG C (temperature higher than Tg) (comparative example 2), although the flexible polyimides with sufficient intensity (mechanical strength) can be obtained, but transmitance is 84%, the most abundant from the aspect of light transmission.So understand, do not use any acid imide agent, when heating attempt hot-imide with the temperature conditionss of 350 DEG C (comparative example 2), it is not necessary to coloring can be adequately suppressed, thus the polyimides with the highest light transmission cannot be manufactured.Result from this comparative example 1 and 2, such as the system not utilizing any acid imide agent used in above-mentioned comparative example, the polyimides with sufficient flexibility cannot be obtained during with 300 DEG C of heating about 1 hour, in order to obtain the polyimides with sufficient flexibility, need to impose heating (using the heating of 350 DEG C in comparative example 2) at higher temperature, thus heating-up temperature when polyimides manufactures cannot be reduced fully.

Additionally, from above-mentioned result, in the case of using acid imide agent, also pyridine and (comparative example 3 and 4) during halogen carboxylic acid anhydrides (trifluoroacetic anhydride) it are applied in combination, even if during with the high-temperature heating of 350 DEG C, the flexible polyimides with sufficient intensity also cannot be formed.Further, in the case of using acid imide agent, also aliphatic category tertiary amine (triethylamine) and (comparative example 5～7) during acetic anhydride it are applied in combination, formed polyimides can be made to become fragile with the heating-up temperatures of 200 DEG C or 300 DEG C (comparative example 5 and 6), thus flexible thin film cannot be obtained, and the heating-up temperature of the high temperature by 350 DEG C as used in comparative example 7, first can obtain flexible thin film.It addition, the heating-up temperature of 350 DEG C is the temperature identical with the heating-up temperature used in usual hot-imide.Additionally, when heating attempt hot-imide with the temperature conditionss of 350 DEG C (comparative example 7), owing to the mean transmissivity of obtained polyimides is 85%, therefore, when using the heating temperature condition of 350 DEG C (comparative example 7), understand compared with the embodiment 1～2 (using the heating temperature condition of 200 DEG C) of particularly identical with the manufacture using polyimides monomer, coloring may not be adequately suppressed, the polyimides with the highest light transmission may not be manufactured.It addition, in the case of using acid imide agent, when being also applied in combination the system of pyridine, acetic anhydride (comparative example 8), it is impossible to coating mixture, thus the polyimides of film like cannot be manufactured.

If it is considered that the result of the manufacture example described in above-mentioned comparative example 1～8, in the case of understanding instant use acid imide agent, when could be used without being applied in combination halogen carboxylic acid anhydrides with the system of the comparative example 1～8 of aliphatic category triamine, will be unable to fully use chemical imidization, in order to manufacture the polyimides with sufficient flexibility, need the heating of higher temperatures (such as high than 300 DEG C temperature).

The probability utilized in industry

As explained above, according to the present invention, can provide and can utilize chemical imidization method and the ester ring type polyimides with the highest thermostability can be manufactured, the polyimides of sufficient flexibility can be had with relatively low-temperature heat manufacture, the coloring of polyimides when can more reliably prevent from manufacturing, and the heating-up temperature that can use more low temperature more effectively and positively manufactures has the highest light transmission, the manufacture method of the highest thermostability and the sufficiently polyimides of the polyimides of flexibility, and by the polyimides obtained by this manufacture method.

So, by the manufacture method of the polyimides of the present invention, can be difficult to, with prior art, the Low Temperature Thermal imidizate reached, by coloring suppression to Min., therefore, it is possible to give the polyimides of the extremely excellent transparency.Therefore, the manufacture method of the polyimides of the present invention is as the polyimides manufacturing the liquid crystal orientation film such as requiring the highest transparency；The polyimides of the transparent electrode substrate of organic EL (bottom emissive type, top emission structure, Clairvoyant type etc.)；The polyimides of organic EL illuminating；The polyimides of the transparent electrode substrate of touch screen；The polyimides of the transparent electrode substrate of solaode；The polyimides of the transparent electrode substrate of Electronic Paper；The polyimides that the clear polyimides of used in copy machines is used for conveyer belt；Various air blocking thin film baseplate materials；The polyimides of flexible wiring substrate；The polyimides of high temperature insulation adhesive tape；The polyimides of electric wire paint；The polyimides of the protective coating of quasiconductor；FPC, photoconduction, imageing sensor, LED reflection plate, LED illumination lid, matrix type FPC, protecting film, chip on film, high ductibility complex substrate, liquid crystal orientation film, polyimide coating material (DRAM, flash memory, the cushioning layer materials of a new generation LSI etc.), the polyimides of formation material towards thin film used in the purposes of the resist of quasiconductor, various electric materials etc.；Particularly useful for manufacturing the method for the raw materials (polyimides) used such as the polyimides of the starting compound (starting monomer) of the material etc. of the various batteries such as lithium ion battery etc..

Claims

1. a manufacture method for polyimides, wherein,

Use contains: have the polyamic acid of repetitive represented by following formula (1), halogen carboxylic acid anhydrides and the mixture of aliphatic category tertiary amine, by by described polyamic acid imidizate, thus obtain the polyimides with the repetitive represented by following formula (2)

In formula (1), R¹Represent and replace the group in basic group, R selected from the tetravalence represented by following formula (I-1)～(I-10)²Represent the group in the bivalent substituted basic group represented by following formula (II-1)～(II-4),

In formula, R³Representing the one in the alkyl that hydrogen atom, carbon number are 1～10 and fluorine atom independently of one another, Q represents selected from formula :-O-,-S-,-CO-,-CONH-,-SO₂-、-C(CF₃)₂-、-C(CH₃)₂-、-CH₂-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-O-C₆H₄-SO₂-C₆H₄-O-、-C(CH₃)₂-C₆H₄-C(CH₃)₂-、-O-C₆H₄-C₆H₄-O-and-O-C₆H₄The one in group represented by-O-,

In formula (2), R¹And R²Respectively with the R in described formula (1)¹And R²Identical meanings.

2. the manufacture method of polyimides as claimed in claim 1, wherein,

By in the operation of described polyamic acid imidizate, it is included in the operation heating described mixture at a temperature of lower than the glass transition temperature of described polyimides 80～300 DEG C.

3. the manufacture method of polyimides as claimed in claim 1 or 2, wherein,

In described mixture, being 1 mole relative to the repetitive of described polyamic acid, the content ratio of described halogen carboxylic acid anhydrides is 0.01～4.0 mole.

4. the manufacture method of the polyimides as according to any one of claims 1 to 3, wherein,

In described mixture, being 1 mole relative to the repetitive of described polyamic acid, the content ratio of described aliphatic category tertiary amine is 0.01～4.0 mole.

5. the manufacture method of the polyimides as according to any one of Claims 1 to 4, wherein,

Farther include by making the tetracarboxylic dianhydride represented by following formula (3) react with the aromatic diamine represented by following formula (4) in organic solvent, thus obtain the operation of described polyamic acid,

In formula (3), R¹With the R in described formula (1)¹Identical meanings,

H₂N-R²-NH₂(4)

In formula (4), R²With the R in described formula (1)²Identical meanings.

6. the manufacture method of the polyimides as according to any one of Claims 1 to 5, wherein,

Described halogen carboxylic acid anhydrides is at least one in the mixed acid anhydride of trifluoroacetic anhydride, difluoroacetic acid acid anhydride, Fluoroethanoic acid acid anhydride, PFPA, heptafluorobutyric anhydride, Trichloroacetic anhydride, dichloroacetic acid acid anhydride, monochloroacetic acid anhydride, tribromoacetic acid acid anhydride, dibromoacetic acid acid anhydride, bromoacetic acid acid anhydride, chlorine difluoroacetic acid acid anhydride, chlorine tetrafluoro propionic andydride, chlorine hexafluoro butyryl oxide. and the acid forming these acid anhydrides.

7. the manufacture method of the polyimides as according to any one of claim 1～6, wherein,

Described aliphatic category tertiary amine is the tertiary amine represented by following formula (5),

In formula (5), R³Represent the alkyl that carbon number is 1～10 independently of one another.

8. a polyimides, wherein,

It it is the polyimides obtained by the manufacture method by the polyimides according to any one of claim 1～7.