JP2017155163A - Tetracarboxylic acid dianhydride, polyimide and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tetracarboxylic acid dianhydride that makes it possible to produce a polyimide having a sufficiently high level of heat resistance, with improved reliability.SOLUTION: A tetracarboxylic acid dianhydride comprises a compound represented by the general formula (1) [where, R, R, Rindependently represent a hydrogen atom or the like, n is an integer of 0-12], with a content of Cu being 10 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a tetracarboxylic dianhydride, a polyimide, and a method for producing the same.

  Conventionally, glass substrates have been used in various fields as substrates (for example, substrates for mobile devices such as smartphones and tablet terminals). However, since the glass substrate has a problem that it is broken by an impact, there has been a demand for the appearance of a light and flexible material having a sufficiently high light transmittance and a sufficiently high heat resistance. An alicyclic polyimide has attracted attention as a material used for such glass substitute applications.

  As such an alicyclic polyimide, for example, in International Publication No. 2011/099518 (Patent Document 1), a polyimide having a repeating unit described by a specific general formula and a tetracarboxylic acid that can be used as a monomer thereof. Acid dianhydrides are disclosed. The polyimide described in Patent Document 1 has a sufficiently high light transmittance and a sufficiently excellent heat resistance, and can be suitably used for glass substitute applications and the like. However, depending on the application, it may be desired to exhibit a high level of heat resistance with polyimide, and the technique described in Patent Document 1 has a sufficiently high level to meet such a requirement. In terms of more reliably producing a heat-resistant polyimide, it is not always sufficient.

International Publication No. 2011/099518

  The present invention has been made in view of the above-described problems of the prior art, and tetracarboxylic dianhydride that makes it possible to more reliably produce a polyimide having a sufficiently high level of heat resistance. It aims at providing the polyimide which has a high level heat resistance, and the manufacturing method of the polyimide.

  The inventors of the present invention made extensive studies to achieve the above object. As a result, first, various metal components that can be contained in tetracarboxylic dianhydride (for example, a catalyst, an oxidant, a reaction vessel used in the production) Among them, it has been found that the content of Cu is related to the heat resistance of the polyimide obtained using the tetracarboxylic dianhydride (in general, The tetracarboxylic dianhydride represented by the following general formula (1) needs to use a copper compound as an oxidizing agent together with a catalyst in its industrial synthesis, and is finally derived from such a copper compound. The copper (Cu) may be contained in the tetracarboxylic dianhydride that is a product. And based on such knowledge, as a result of further earnest studies to achieve the above object, the present inventors are represented by the following general formula (1) in which the Cu content is 10 ppm or less. Surprisingly, it has been found that such a tetracarboxylic dianhydride can more reliably (more stably) produce a polyimide having a sufficiently high level of heat resistance. It came to complete.

  That is, the tetracarboxylic dianhydride of the present invention has the following general formula (1):

[In the formula (1), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom; An integer of 12 is shown. ]
And a compound represented by
The content of Cu (copper) is 10 ppm or less.

  In the tetracarboxylic dianhydride of the present invention, the content of Pd (palladium) is preferably 10 ppm or less.

  In the tetracarboxylic dianhydride of the present invention, the B (boron) content is preferably 5 ppm or less.

The polyimide of the present invention includes the tetracarboxylic dianhydride of the present invention and the following general formula (3):
^{_{H 2 N-R 10 -NH 2}} (3)
[In the formula (3), R ¹⁰ represents an aryl group having 6 to 50 carbon atoms. ]
And a polymer with an aromatic diamine represented by the following general formula (2):

[In the formula (2), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R ¹⁰ represents carbon. An aryl group having a number of 6 to 50 is shown, and n is an integer of 0 to 12. ]
It is characterized by containing the repeating unit represented by these.

The method for producing the polyimide of the present invention comprises the above tetracarboxylic dianhydride of the present invention and the following general formula (3):
^{_{H 2 N-R 10 -NH 2}} (3)
[In the formula (3), R ¹⁰ represents an aryl group having 6 to 50 carbon atoms. ]
After forming a polyamic acid by reacting with an aromatic diamine represented by the following, by imidizing the polyamic acid,
It is a polymer of the tetracarboxylic dianhydride and the aromatic diamine, and the following general formula (2):

Wherein ^{(2), R 1, R} 2, R 3 are each independently a hydrogen atom, it represents one selected from the group consisting of alkyl groups and fluorine atom having 1 to 10 carbon ^{atoms, R 10} is A C6-C50 aryl group is shown, n shows the integer of 0-12. ]
Obtaining a polyimide containing a repeating unit represented by:
It is the method characterized by this.

  According to the present invention, a tetracarboxylic dianhydride that makes it possible to more reliably produce a polyimide having a sufficiently high level of heat resistance, a polyimide having a sufficiently high level of heat resistance, and its It is possible to provide a method for producing polyimide.

6 is a graph showing an IR spectrum of the polyimide obtained in Example 5.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Tetracarboxylic dianhydride]
The tetracarboxylic dianhydride of the present invention has the following general formula (1):

[In the formula (1), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom; An integer of 12 is shown. ]
And a compound represented by
The content of Cu (copper) is 10 ppm or less.

The alkyl group that can be selected as R ¹ in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. When such a carbon number exceeds 10, when it uses as a monomer of a polyimide, the heat resistance of the polyimide obtained will fall. As the number of carbon atoms in the alkyl group such can be selected as R ^1, from the viewpoint of high heat resistance when a polyimide was prepared to obtain, preferably 1 to 6, is 1 to 5 Is more preferable, it is still more preferable that it is 1-4, and it is especially preferable that it is 1-3. Such an alkyl group that can be selected as R ¹ may be linear or branched.

R ¹ in the general formula (1) is more preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms from the viewpoint of obtaining a high degree of heat resistance when a polyimide is produced. Among these, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group is more preferable from the viewpoint of easy availability of raw materials and easier purification, and a hydrogen atom or methyl group is more preferable. Particularly preferred is a group. Moreover, it is especially preferable that several R < ¹ > in such a formula is the same from viewpoints of the ease of refinement | purification etc.

The alkyl group having 1 to 10 carbon atoms R ^2, may be selected as R ³ in the general formula (1) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ¹ described above Is. As such substituents that can be selected as R ² and R ³ , from the viewpoint of ease of purification, each of the above substituents is independently a hydrogen atom, a C 1-10 (preferably 1-6, The alkyl group is more preferably 1 to 5, still more preferably 1 to 4, particularly preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

  Moreover, n in the said General formula (1) shows the integer of 0-12. When the value of n exceeds the above upper limit, norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic Purification of acid dianhydrides becomes difficult. Further, the upper limit value of the numerical value range of n in the general formula (1) is more preferably 5 and particularly preferably 3 from the viewpoint of easier purification. Further, the lower limit of the numerical range of n in the general formula (1) is more preferably 1 and particularly preferably 2 from the viewpoint of the stability of the raw material. Thus, it is particularly preferable that n in the general formula (1) is an integer of 2 to 3.

  The tetracarboxylic dianhydride of the present invention is such a compound represented by the general formula (1) and has a Cu content of 10 ppm or less. First, the compound represented by the above general formula (1) (tetracarboxylic dianhydride) is, for example, as shown in Example 1 of International Publication No. 2011/099518. It is produced by using the compound as an oxidizing agent. In particular, from the viewpoint of industrial production, a copper compound is generally used as an essential component because of the availability of an oxidizing agent, its effect, etc. It is used in producing a tetracarboxylic acid ester compound that is a precursor of an anhydride). And the said tetracarboxylic dianhydride which is a final product derived from the copper compound utilized at the time of such manufacture may contain copper (Cu). Under such circumstances, the tetracarboxylic dianhydride of the present invention has a Cu content of 10 ppm or less. When such Cu content exceeds the upper limit, the heat resistance of the polyimide obtained using such a tetracarboxylic dianhydride tends to decrease. Further, since higher heat resistance is obtained, the content of Cu in the tetracarboxylic dianhydride is more preferably 5 ppm or less, further preferably 3 ppm or less, and 2 ppm or less. Is particularly preferred, with 1 to 0 ppm being most preferred. Depending on the type of the tetracarboxylic dianhydride and the type of the copper compound used during the production of the compound, the content of such Cu may be determined based on the tetracarboxylic dianhydride and its precursor (tetracarboxylic acid ester). In the production of the compound, etc.), the filtration range, the washing step and the purification step can be carried out as appropriate so that the above range is satisfied.

  In addition, the compound represented by the above general formula (1) (tetracarboxylic dianhydride) generally uses a palladium catalyst for its industrial production (in particular, tetracarboxylic dianhydride). It is used when producing a tetracarboxylic acid ester compound as a precursor.) Therefore, the tetracarboxylic dianhydride of the present invention can contain palladium (Pd) derived from the catalyst. And in the tetracarboxylic dianhydride of the present invention, the content of palladium that can be included in the production is preferably 10 ppm or less, more preferably 8 ppm or less, still more preferably 6 ppm or less, 5 ppm or less is particularly preferable, and 3 to 0 ppm is most preferable. If the Pd content exceeds the upper limit, a polyimide having a sufficiently high level of transparency tends to be not obtained. The content of such Pd depends on the type of tetracarboxylic dianhydride, the type of catalyst used during the production of the compound, etc., and the precursor thereof (tetracarboxylic acid ester compound). Etc.) can be made within the above range by appropriately performing a filtration step, a washing step and a purification step.

In addition, the compound represented by the above general formula (1) (tetracarboxylic dianhydride) is generally industrially obtained after obtaining a tetracarboxylic acid ester compound using a palladium catalyst, a copper compound, etc. It is manufactured by adopting a method of converting a tetracarboxylic acid ester compound into an acid anhydride. And in such acid anhydride formation, in order to obtain a more transparent compound more efficiently, tetrafluoroethanesulfonic acid (HCF ₂ CF ₂ SO ₃ H, boiling point: 210 ° C.) which is a super strong acid, etc. Or a homogeneous catalyst (for example, a homogeneous catalyst described in JP-A-2015-218160) is used. And when such a super strong acid is utilized, boron may be contained in the tetracarboxylic dianhydride finally obtained by eluting a small amount (trace amount) of boron from a flask or the like used as a reaction vessel. . That is, boron is a component contained in a reaction vessel such as a flask (Pyrex (registered trademark) glass) and the like, and when producing a compound represented by the above general formula (1) (tetracarboxylic dianhydride). In particular, it is a component that can be eluted from a reaction vessel (flask (Pyrex (registered trademark) glass)) and mixed into the compound in a step of utilizing an acid such as a super strong acid. In the tetracarboxylic dianhydride of the present invention, the content of boron (B) mixed as described above is preferably 5 ppm or less, more preferably 4 ppm or less, and 3 ppm or less. More preferably, it is more preferably 2 ppm or less, and most preferably 1 to 0 ppm. When the B content exceeds the upper limit, a polyimide having a sufficiently high level of heat resistance tends to be not obtained. Further, the content of such boron (B) depends on the type of the tetracarboxylic dianhydride, etc., during the production of the tetracarboxylic dianhydride and its precursor (tetracarboxylic ester compound, etc.) By appropriately performing a filtration step, a washing step (especially a water washing step) and a purification step, it can be within the above range (in addition, since boron (B) generally uses an acid in an acid anhydride step, an acid anhydride). Since it is a component that easily mixes in the materialization process, in order to satisfy the above requirements for the boron content, after the preparation of tetracarboxylic dianhydride, the filtration process, the washing process (especially the water washing process) and the purification process It is more preferable to carry out as appropriate.)

  In the present invention, the content of the metal components (Cu, Pd, B) that can be contained in the tetracarboxylic dianhydride is determined as an ICP emission spectroscope (for example, trade name “iCap630 Duo manufactured by Thermo Fisher Co., Ltd.) as a measuring device. )) As a sample, a tetracarboxylic dianhydride 0 was added as a sample in a mixed solution of 96% by mass ultrapure sulfuric acid aqueous solution (1 mL) and 60% by mass ultrapure perchloric acid aqueous solution (2 mL). After dissolving 2 g, prepare a solution diluted with ultrapure water so that the total amount becomes 50 mL, and in the solution (sample) under conditions of axial photometry (axial) and measurement time 30 seconds By analyzing the amount of each metal component, it can be measured by determining the content (unit: ppm) of each metal component in the compound (tetracarboxylic dianhydride) based on mass. The ultra-high purity reagents such as “ultra-high purity sulfuric acid aqueous solution”, “ultra-high purity perchloric acid aqueous solution”, and “ultra-pure water” are used to detect the content of impurity elements by ICP and ICP-MS devices. It is a solution purified to below the limit (ppt level), and as these aqueous solutions and the like, commercially available products (for example, ultra-pure reagent Ultrapure series manufactured by Kanto Chemical Co., Inc.) can be used as appropriate.

  Although it does not restrict | limit especially as a method for manufacturing such tetracarboxylic dianhydride of this invention, For example, following General formula (4-1):

^[R 1 in the formula ^{(4-1), R 2, R} 3, n are respectively the same as ^{R 1, R 2, R 3} , n in the general formula (1) (same as the preferred ]]]
In the presence of a palladium catalyst and a copper compound, a carbon atom (general formula) that forms a double bond in the above general formula (4-1). In (4-1), carbon atoms represented by * 1 to * 4) are each introduced with an ester group to form a tetracarboxylic acid ester compound (crude product). When the acid anhydride is formed, the crude product is appropriately subjected to a filtration step and a washing step so that the content of Cu (copper) in the resulting tetracarboxylic dianhydride is 10 ppm or less, A method of obtaining a tetracarboxylic dianhydride by converting the compound (tetracarboxylic acid ester compound) obtained after appropriately performing the filtration step and the washing step into an acid anhydride is suitably used. It can be. In such a method, for example, the alcohol is represented by the formula: ROH [wherein R represents an alkyl group or the like. ] Is introduced into the carbon atom forming the double bond in the general formula (4-1) (the carbon atom represented by * 1 to 4 in the general formula (4-1)). The ester group to be represented is represented by the formula: —COOR, and the resulting tetracarboxylic acid ester compound is represented by the following formula (4-2):

^[R 1 in the formula ^{(4-2), R 2, R} 3, n are respectively the same as ^{R 1, R 2, R 3} , n in the general formula (1) (same as the preferred R is a group derived from the alcohol used (for example, when the formula ROH (methanol) in which R is a methyl group is used as the alcohol, R is a methyl group). ]
It becomes the compound represented by these.

  Such a norbornene-based compound represented by the general formula (4-1) can be produced by appropriately employing a known method (for example, a method described in International Publication No. 2011/099518). .

  In addition, the alcohol is not particularly limited, and any alcohol that can be used for esterification can be appropriately used. Among them, from the viewpoint of industrial availability, the number of carbon atoms is 1 to 10. It is preferable to use an alkyl alcohol of 3 to 10 carbon atoms, a cycloalkyl alcohol having 3 to 10 carbon atoms, an alkenyl alcohol having 2 to 10 carbon atoms, an aryl alcohol having 6 to 20 carbon atoms, and an aralkyl alcohol having 7 to 20 carbon atoms. Specific examples of such alcohols include methanol, ethanol, butanol, allyl alcohol, cyclohexanol, benzyl alcohol, etc. Among them, methanol and ethanol are preferred from the viewpoint that purification of the resulting compound is easier. Is more preferable, and methanol is particularly preferable. Such alcohols may be used alone or in combination of two or more.

  In addition, the method for forming a tetracarboxylic acid ester compound by reacting with carbon monoxide and an alcohol in the presence of a palladium catalyst and a copper compound (conditions for forming) is not particularly limited, and a known method (for example, The methods described in International Publication No. 2011/099518, Japanese Patent Application Laid-Open No. 2015-137230, and the like can be appropriately employed.

  Such a palladium catalyst or copper compound is not particularly limited, and can be used to introduce an ester group into a carbon atom that forms a double bond. Palladium catalysts described in 2011/099518 and International Publication No. 2014/050810, and copper compounds exemplified as oxidizing agents in International Publication Nos. 2011/099518 and 2014/050810 (for example, copper chloride, copper acetate) , Copper carbonate, etc.) can be used as appropriate.

  In addition, after reacting with carbon monoxide and alcohol to form a tetracarboxylic acid ester compound to obtain a crude product of the tetracarboxylic acid ester compound, the tetracarboxylic acid ester compound is converted into an acid as described above. Before the anhydride, the crude product of the tetracarboxylic acid ester compound is filtered and washed so that the content of Cu (copper) in the finally obtained acid dianhydride is 10 ppm or less. It is preferable to perform the process appropriately. Such a filtration process and a washing | cleaning process are the quantity of the metal component which can be mixed at the time of manufacture (for example, content of Cu mixed from the said copper compound, content of Pd mixed from the said palladium catalyst, etc.) ) May be appropriately implemented so as to be within a desired range, and depending on the type of compound to be obtained and the type of metal that can be mixed, known methods and conditions are appropriately adopted, the amount of metal component (for example, The content of Cu, the content of Pd, etc.) may be within the target ranges.

  Further, as such a filtration step, from the viewpoint of efficiently removing metal components such as Cu and Pd, the tetracarboxylic acid ester compound can be dissolved, but the palladium catalyst or copper compound used in the production of the compound can be dissolved. It is preferable to set it as the process of removing a palladium catalyst and a copper compound by dissolving, after filtering the said crude product in the solvent which cannot melt | dissolve. In addition, it does not restrict | limit especially as such a filtration process, A well-known method (For example, the method of Unexamined-Japanese-Patent No. 2015-137230) can be employ | adopted suitably.

  In addition, the washing step is not particularly limited, and as an impurity that can be mixed during production by appropriately combining a washing step using a halogen-based solvent (such as chloroform) or hydrochloric acid, a washing step using water, and the like. What is necessary is just to implement suitably according to the kind of the used catalyst, the kind of obtained compound, etc. so that the quantity (for example, content of Cu, content of Pd, etc.) of this may become a desired range. . Depending on the type of catalyst used and the type of compound obtained, for example, the number of water washing steps is adjusted so that the amount of metal component (eg, Cu content, Pd content, etc.) is in the desired range. What is necessary is just to implement a washing | cleaning process, changing the conditions, such as the frequency | count of implementation of a washing | cleaning process, the quantity of the water to be used, etc. suitably, such as making it into multiple times.

  Moreover, after implementing such a filtration process and a washing | cleaning process, you may further give a refinement | purification process as needed from a viewpoint of obtaining a compound of higher purity. As a purification method, for example, a step of adding a tetracarboxylic acid ester compound in acetic acid, dissolving it by heating, and then allowing to cool and precipitating crystals of the tetracarboxylic acid ester compound (acetic acid recrystallization). A crystallization step) may be used.

Further, the method of acidifying the tetracarboxylic acid ester compound is not particularly limited, and known methods (for example, International Publication Nos. 2011/099518, JP-A-2015-137234, and JP-A-2015-218160) However, from the viewpoint of more efficiently producing a highly transparent tetracarboxylic dianhydride, it is possible to employ a so-called homogeneous catalyst (as a catalyst). It is particularly preferable to employ a method of acid dianhydride utilizing a super strong acid (for example, a method described in JP-A-2015-218160). And when adopting the method of acid dianhydride using super strong acid as such a homogeneous catalyst, the metal component (particularly boron (B)) contained in the reaction vessel by the super strong acid Since it is dissolved and mixed, the filtration step and the washing step (for example, acetic acid) are performed so that the content of metal components (Cu, Pd, B, etc.) that can be mixed after the acid anhydride is within a desired range. In addition to a washing step using ethyl, etc., it is preferable to carry out a purification step and the like as appropriate. In addition, as such a filtration process, washing | cleaning process, and a refinement | purification process after acid anhydride formation, according to the kind of compound obtained and the kind (Cu, Pd, B, etc.) which can be mixed, well-known method and conditions May be adopted as appropriate, and the conditions may be changed appropriately so that the content of the metal component falls within the target range. In addition, for example, from the viewpoint that the content of boron (B) is within the above range, a solution having high solubility of acetic acid as a reaction solvent or an eluted boron component (for example, ethyl acetate or the like) is used. It is preferable to wash the tetracarboxylic dianhydride obtained by the materialization (Note that the content of boron (B) is within the above range by appropriately changing the conditions such as the amount of the washing liquid used and the number of washings) The desired amount can be obtained.)
Thus, after obtaining a crude product of a tetracarboxylic acid ester compound, a filtration step, a washing step, and optionally a purification step such as recrystallization are appropriately performed to obtain a tetracarboxylic acid ester compound. Is converted to an acid anhydride (optionally, even after acid anhydride conversion, the filtration step, the washing step, the purification step, etc. are performed as appropriate), the Cu content is 10 ppm or less, and the above general formula (1 ) Can be efficiently obtained. In addition, by appropriately changing the conditions of the filtration step, the washing step, and the recrystallization step applied to the crude product of the tetracarboxylic acid ester compound and the tetracarboxylic dianhydride obtained after acid anhydride formation, Not only can the content be 10 ppm or less, but the palladium content can be 10 ppm or less, and the boron content can be 5 ppm or less. In addition, what is necessary is just to set suitably the conditions which are employ | adopted by the well-known method according to the kind etc. of the catalyst used for the conditions of such a filtration process, a washing | cleaning process, and a recrystallization process.

  In addition, the method suitable as a method for manufacturing the above-mentioned tetracarboxylic dianhydride is a method of subjecting a crude product of a tetracarboxylic acid ester compound to a filtration step, a washing step, a recrystallization step, etc. Even after acid anhydride formation, the filtration step, washing step, purification step and the like were appropriately performed), but the method for producing the tetracarboxylic dianhydride of the present invention is not limited to the above method. For example, after a tetracarboxylic acid ester compound is obtained, and then converted into an acid anhydride, a tetracarboxylic acid diester is prepared so that the content of Cu is 10 ppm or less by appropriately performing a filtration step, a washing step, and a recrystallization step. It is good also as a method of obtaining an anhydride. Also in this case, the filtration step, the washing step, the recrystallization step, etc. are appropriately performed according to the target design under known conditions (the conditions are appropriately set so that the content of Cu, Pd, and further B becomes a desired amount. Can be implemented while changing

[Polyimide]
The polyimide of the present invention includes the tetracarboxylic dianhydride of the present invention and the following general formula (3):
^{_{H 2 N-R 10 -NH 2}} (3)
[In the formula (3), R ¹⁰ represents an aryl group having 6 to 50 carbon atoms. ]
And a polymer with an aromatic diamine represented by the following general formula (2):

[In the formula (2), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R ¹⁰ represents carbon. An aryl group having a number of 6 to 50 is shown, and n is an integer of 0 to 12. ]
It is characterized by containing the repeating unit represented by these.

Such an aromatic diamine has the following general formula (3):
^{_{H 2 N-R 10 -NH 2}} (3)
It is represented by The aryl group that can be selected as R ¹⁰ in the general formula (3) has 6 to 50 carbon atoms, and the aryl group preferably has 6 to 40 carbon atoms, More preferably, it is 6-30, and it is still more preferable that it is 12-20. When the number of carbon atoms is less than the lower limit, the heat resistance of the resulting polyimide tends to be reduced. On the other hand, when the carbon number exceeds the upper limit, the solubility of the obtained polyimide in a solvent tends to be lowered.

As the ^{R 10} in the general formula (3), from the viewpoint of balance of solubility and heat resistance, the following general formula (5) to (8):

[In the formula (7), R ¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group, and in the formula (8), Q represents a formula: _{-O -, - S -, -} CO -, - CONH -, - SO 2 -, - C (CF 3) 2 -, - C (CH 3) 2 -, - CH 2 -, - O-C 6 H _{4 -C (CH 3) 2 -C} 6 H 4 -O -, - O-C 6 H 4 -C (CF 3) 2 -C 6 H 4 -O -, - O-C 6 H 4 -SO 2 _{-C 6 H 4 -O -, -} C (CH 3) 2 -C 6 H 4 -C (CH 3) 2 -, - O-C 6 H 4 -C 6 H 4 -O-, and, -O -C ₆ H ₄ -O-, a group represented by the well, the following general formula (9):

(In the formula (9), R ^a independently represents any one of an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a tolyl group, and y represents an integer of 1 to 18.)
1 type selected from the group consisting of groups represented by: ]
It is preferable that it is at least 1 sort (s) of group represented by these.

R ¹¹ in the general formula (7) is more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom, from the viewpoint of heat resistance.

In the group represented by the general formula (9) that can be selected as Q in the general formula (8), each R ^a is independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a tolyl group. Any one of these. When the carbon number of such an alkyl group exceeds the upper limit, the heat resistance and transparency of the polyimide film tend to be reduced. Such ^Ra is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a tolyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

  Moreover, y in the said General formula (9) shows the integer of 1-15 (more preferably 3-12, still more preferably 5-10). If the value of y is less than the lower limit, the adhesiveness and laser peelability of the polyimide film (ease of film peeling when laser peeling treatment is performed when a film is formed on a substrate) tend to decrease. On the other hand, when the upper limit is exceeded, the heat resistance and transparency of the polyimide film tend to be lowered.

In addition, the aromatic in which R ¹⁰ in the general formula (3) is a group represented by the formula (8), and Q in the formula (8) is a group represented by the general formula (9). As a suitable example of the group diamine, for example, the following formula (10):

[In the formula (10), Me represents a methyl group. ]
(Silicone-based aromatic diamine) and the like.

As the Q in the general formula (8), from the viewpoint of solubility of the balance between heat resistance, the _{formula: -CONH -, - O-C} 6 H 4 -O -, - O -, - C (CH _{3) 2 -, - CH 2} -, - O-C 6 H 4 -C 6 H 4 -O- , or _{-O-C 6 H 4 -C (} CH 3) 2 -C 6 H 4 -O-, in Groups represented by the formula: —CONH—, —O—C ₆ H ₄ —O—, —O—C ₆ H ₄ —C ₆ H ₄ —O— or —O— are particularly preferred. A group represented by the formula: —CONH—, —O—C ₆ H ₄ —O— or —O— is most preferable. Furthermore, Q in the general formula (8) is preferably a group represented by the general formula (9) from the viewpoints of adhesiveness and laser peelability, and has a linear expansion coefficient and heat resistance. Is preferably a group represented by the formula: -CONH-.

  Examples of the aromatic diamine represented by the general formula (3) include 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 3,3. '-Diaminodiphenylethane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) Propane, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-amino Phenoxy) phenyl] sulfone, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphe , 3,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 9,9-bis (4-aminophenyl) fluorene, p-diaminobenzene, m-diaminobenzene, o -Diaminobenzene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 3,3'-diaminobiphenyl, 2,2′-diaminobiphenyl, 3,4′-diaminobiphenyl, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4 ′-[1,3-phenylenebis ( 1-methyl-ethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] Suaniline, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminobenzanilide, 3,4′- Diaminobenzanilide, 9,9′-bis (4-aminophenyl) fluorene, o-tolidine sulfone, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3 ′, 5,5 ′ -Tetramethylbenzidine, 1,5-bis (4-aminophenoxy) pentane, 2,2-bis (4-aminophenoxyphenyl) hexafluo And ropropane. Among such aromatic diamines, 4,4′-diaminobenzanilide, p-diaminobenzene, 2,2′-dimethyl-4 are preferred from the viewpoints of surface smoothness, heat resistance, transparency, and linear expansion coefficient. 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl are preferred, 4,4′-diaminobenzanilide, p-diamino Benzene and 4,4′-bis (4-aminophenoxy) biphenyl are more preferable, and 4,4′-diaminobenzanilide and p-diaminobenzene are still more preferable. Such aromatic diamines may be used alone or in combination of two or more in accordance with the design of the target polyimide.

  The polyimide of the present invention is a polymer of the tetracarboxylic dianhydride of the present invention and an aromatic diamine represented by the general formula (3). Thus, since the polyimide of the present invention is a polymer obtained by using the tetracarboxylic dianhydride of the present invention as a monomer, derived from the tetracarboxylic dianhydride of the present invention, The content of Cu contained in the polyimide can be made sufficiently low, and the heat resistance of the polyimide can be made higher. In addition, the manufacturing conditions etc. of such a polymer are demonstrated in the manufacturing method of the polyimide of this invention mentioned later.

  Furthermore, the polyimide of the present invention is a polymer of the tetracarboxylic dianhydride of the present invention and an aromatic diamine represented by the above general formula (3), which has the following general formula (2):

[In the formula (2), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R ¹⁰ represents carbon. An aryl group having a number of 6 to 50 is shown, and n is an integer of 0 to 12. ]
The repeating unit represented by these is contained.

^{R 1,} R ^{2, R} 3, n in the general formula (2) is respectively the same as ^{R 1,} R ^{2, R} 3, n in the general formula (1), the preferred The same is true for anything. R ¹⁰ in the general formula (2) is a group derived from the aromatic diamine represented by the general formula (3), and is the same as R ¹⁰ in the general formula (3). (The same applies to the preferred ones.)

  Further, as such a polyimide, from the viewpoint of heat resistance, the content of Cu in the polyimide is more preferably 5 ppm or less, further preferably 3 ppm or less, particularly preferably 2 ppm or less, Most preferably, it is 1 to 0 ppm. Furthermore, as such a polyimide, from the viewpoint of obtaining a polyimide having a higher level of transparency, the content of Pd in the polyimide is more preferably 8 ppm or less, and further preferably 6 ppm or less. It is particularly preferably 5 ppm or less, and most preferably 3 to 0 ppm. Further, as such polyimide, from the viewpoint of obtaining a polyimide having a higher level of heat resistance, the content of B in the polyimide is more preferably 4 ppm or less, and further preferably 3 ppm or less. 2 ppm or less is particularly preferable, and 1 to 0 ppm is most preferable.

  Moreover, as such a polyimide, that whose 5% weight loss temperature is 490 degreeC or more is preferable, and the thing of 500 to 550 degreeC is more preferable. If the 5% weight loss temperature is less than the lower limit, it tends to be difficult to obtain a very high heat resistance as required in the present invention. It tends to be difficult to produce a polyimide having the above. Such a 5% weight reduction temperature is obtained by using a thermogravimetric analyzer (for example, trade name “TG / DTA220” manufactured by SII Nano Technology Co., Ltd.) as a measuring device, and scanning temperature in a nitrogen gas atmosphere. Is set to 30 ° C. to 550 ° C., and the rate of temperature increase is 10 ° C./min. The temperature can be determined by measuring the temperature at which the weight of the sample used is reduced by 5%. In the measurement, it is preferable to use the mass of the sample as 1.0 mg to 10 mg. When the mass of the sample is within the above range, the same value can be measured for the same polyimide even if the mass of the sample is changed.

  Moreover, as such a polyimide, from the viewpoint of obtaining a higher degree of transparency, a polyimide having a total light transmittance of 80% or more (more preferably 85% or more, particularly preferably 87% or more) is more preferable. Moreover, as such a polyimide, the thing whose haze (turbidity) is 5-0 (more preferably 4-0, especially preferably 3-0) is more preferable from a viewpoint of obtaining higher transparency. . Furthermore, as such a polyimide, from the viewpoint of obtaining higher transparency, it is more preferable that the yellowness (YI) is 5 to 0 (more preferably 4 to 0, particularly preferably 3 to 0). . Such total light transmittance, haze (turbidity), and yellowness (YI) can be easily achieved by appropriately selecting the type of polyimide. In addition, such total light transmittance, haze (turbidity), and yellowness (YI), as a measuring device, the brand name "Hazemeter NDH-5000" by Nippon Denshoku Industries Co., Ltd. or Nippon Denshoku Industries Co., Ltd. Using the product name “Spectral Color Meter SD6000” manufactured by the company (Nippon Denshoku Industries Co., Ltd., product name “Haze Meter NDH-5000” was used to measure the total light transmittance and haze. The value measured by using a film made of polyimide having a thickness of 5 to 20 μm as a sample for measurement can be adopted. The total light transmittance, haze (turbidity), and yellowness (YI) are the same because the thickness is sufficiently thin and the measured value is not affected if the film is made of polyimide having a thickness of 5 to 20 μm. The same value can be measured from the polyimide. Therefore, what is necessary is just to utilize the film which has the thickness of the said range for the measurement of a total light transmittance, haze (turbidity), and yellowness (YI). In addition, the vertical and horizontal sizes of the measurement sample may be any size that can be arranged at the measurement site of the measurement apparatus, and the vertical and horizontal sizes may be appropriately changed. In addition, such total light transmittance is calculated | required by measuring based on JISK7361-1 (issued in 1997), and a haze (turbidity) performs the measurement based on JISK7136 (issued in 2000). The yellowness (YI) is obtained by performing measurement in accordance with ASTM E313-05 (issued in 2005).

  Further, such a polyimide preferably has a linear expansion coefficient of 0 to 100 ppm / K, more preferably 5 to 60 ppm / K, and still more preferably 10 to 30 ppm / K. When such a linear expansion coefficient exceeds the upper limit, peeling tends to occur due to thermal history when combined with a metal or inorganic material having a linear expansion coefficient range of 5 to 20 ppm / K. Moreover, when the linear expansion coefficient is less than the lower limit, the solubility and the film characteristics tend to be lowered. As a method for measuring the linear expansion coefficient of such polyimide, a polyimide film having a size of 20 mm in length and 5 mm in width (thickness of the film does not affect the measured value, but is not particularly limited. To 30 μm.) To form a measurement sample, and using a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku) as a measurement device, under a nitrogen atmosphere, a tensile mode (49 mN), The length per 1 ° C. in the temperature range of 50 ° C. to 200 ° C. is measured by measuring the change in the length of the sample in the vertical direction at 50 ° C. to 200 ° C. under the condition of the heating rate of 5 ° C./min. The value obtained by calculating the average value of the changes in is adopted.

  Furthermore, the number average molecular weight (Mn) of such a polyimide is preferably 1000 to 100,000 in terms of polystyrene. Moreover, as a weight average molecular weight (Mw) of such a polyimide, it is preferable that it is 1000-500000 in polystyrene conversion. Furthermore, the molecular weight distribution (Mw / Mn) of such a polyimide is preferably 1.1 to 5.0. When such Mn, Mw, Mw / Mn is less than the lower limit, the physical properties of the film tend to be lowered. On the other hand, when the upper limit is exceeded, the viscosity exceeds 5 to 150 cps, and the surface smoothness of the film tends to deteriorate. is there. In addition, the molecular weight (Mw or Mn) and molecular weight distribution (Mw / Mn) of such a polyimide can be obtained by converting measured data with polystyrene using gel permeation chromatography as a measuring device. In addition, in such a polyimide, when it is difficult to measure the molecular weight, the molecular weight is estimated based on the viscosity of the polyamic acid used for the production of the polyimide, and the polyimide according to the application is selected. May be used.

  Moreover, as a polyimide which forms such a film, it is preferable that glass transition temperature is 200 degreeC or more, It is more preferable that it is 250 to 500 degreeC, It is especially preferable to set it as 300 to 450 degreeC. If such a glass transition temperature is less than the lower limit, it tends to be unusable for the intended application (glass replacement, organic EL substrate, etc.) from the viewpoint of heat resistance. The glass transition temperature of such a polyimide is measured using a thermomechanical analyzer (for example, trade name “TMA8311” manufactured by Rigaku) as a measuring device, under a temperature increase rate of 5 ° C./min under a nitrogen atmosphere. A value obtained by scanning between 30 ° C. and 550 ° C. in the penetration mode (measured value by a so-called penetration (needle insertion) method) can be adopted. The following softening temperatures can be measured simultaneously under the same measurement conditions as the glass transition temperature (when a glass transition temperature is detected, a peak appears before the softening temperature).

  Moreover, as such a polyimide, that whose softening temperature is 300 degreeC or more is preferable, and the thing of 350-550 degreeC is more preferable. If the softening temperature is less than the lower limit, it tends to be difficult to obtain sufficient heat resistance, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide having such characteristics. . In addition, such a softening temperature can be measured by a penetration mode using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) (can be measured by a so-called penetration method). In measurement, the sample size (vertical, horizontal, thickness, etc.) does not affect the measured value, so it can be attached to the jig of the thermomechanical analyzer to be used (trade name “TMA8310” manufactured by Rigaku). The sample size may be adjusted as appropriate to a suitable size. In addition, as a measuring method of such a softening temperature, for example, a film made of polyimide having a size of 5 mm in length, 5 mm in width, and 13 μm in thickness is prepared as a measurement sample, and a thermomechanical analyzer (manufactured by Rigaku) is used as a measuring device. Using a product name “TMA8311”), a transparent quartz pin (tip diameter: tip diameter) was applied to the film under a temperature range of 30 ° C. to 550 ° C. under a nitrogen atmosphere under a temperature rising rate of 5 ° C./min. You may employ | adopt the method (what is called penetration (needle insertion) method) which measures by inserting a needle into 0.5 mm.

  Although the polyimide of the present invention has been described above, the method for producing the polyimide of the present invention that can be suitably used as a method for producing the polyimide of the present invention will be described below.

[Production method of polyimide]
The method for producing the polyimide of the present invention comprises forming the polyamic acid by reacting the tetracarboxylic dianhydride of the present invention with the aromatic diamine represented by the general formula (3), By imidizing,
Obtaining a polyimide which is a polymer of the tetracarboxylic dianhydride and the aromatic diamine and contains a repeating unit represented by the general formula (2),
It is the method characterized by this.

  Such a method for producing a polyimide utilizes the tetracarboxylic dianhydride of the present invention (a tetracarboxylic dianhydride of the present invention having a Cu content of 10 ppm or less) as the tetracarboxylic dianhydride. In addition, except that the aromatic diamine represented by the general formula (3) is used as the aromatic diamine, a known polyimide production method (a method described in International Publication No. 2011/099518, International Publication No. 2013/021942). Can be used. Therefore, as the conditions for reacting the tetracarboxylic dianhydride of the present invention with the aromatic diamine represented by the general formula (3), known conditions may be appropriately employed. And a mixture containing the tetracarboxylic dianhydride of the present invention and the aromatic diamine represented by the general formula (3), and an inert atmosphere such as atmospheric pressure, nitrogen, helium, argon The method of making it react by stirring for 0.5 to 24 hours on the conditions of 0-50 degreeC on these conditions may be employ | adopted. Examples of such a solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, propylene carbonate, tetramethylurea (tetramethylurea). (TMU)), aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, pyridine; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol; Ether solvents such as tetrahydrofuran, dioxane, cellosolve, glyme, diglyme and propylene glycol monomethyl ether acetate; aromatic solvents such as benzene, toluene and xylene; ketones such as cyclopentanone and cyclohexanone Emissions solvents; acetonitrile, nitrile solvents such as benzonitrile and the like.

  Further, the polyamic acid obtained by reacting the tetracarboxylic dianhydride of the present invention with the aromatic diamine represented by the general formula (3) as described above is represented by the following general formula (11):

Expression ^{(11) R 1, R 2} , R 3, n in is in each the same as ^{R 1, R 2, R 3} , n in the general formula (1) (same as the preferred in a.), ^{R 10} in the formula (11) is similar to the ^{R 10} in the general formula (3) (the same applies to those that preferred.). ]
It will be represented by Before the imidation described below, the polyamic acid obtained as described above is dissolved in the solvent as it is (in the state where it is present in the solvent when reacted in a solvent) or after isolation. In addition, it may be stored as a solution (resin solution: varnish) containing the polyamic acid and the solvent.

  Further, the method for imidizing such polyamic acid is not particularly limited, and is employed in a known polyimide production method (method described in International Publication No. 2011/099518, method described in International Publication No. 2013/021942). The imidization method (for example, the polyamic acid is heated to 60 to 450 ° C. (more preferably 60 to 400 ° C., further preferably 150 to 350 ° C., particularly preferably 150 ° C. to 250 ° C.) to imidize. Method, etc.) can be employed as appropriate.

  Thus, the polyimide obtained by imidizing the polyamic acid is a polymer of the tetracarboxylic dianhydride of the present invention and the aromatic diamine, and is represented by the general formula (2). It becomes a polyimide containing a repeating unit. And since such a polyimide uses the tetracarboxylic dianhydride of the present invention having a Cu content of 10 ppm or less as a monomer, the content of Cu contained in the obtained polyimide is sufficient. This can reduce the heat resistance of the resulting polyimide. Moreover, according to the manufacturing method of the polyimide of this invention, the said polyimide of this invention can be manufactured efficiently.

  In addition, since the content of Cu is sufficiently suppressed and the polyimide of the present invention has a very high heat resistance, for example, a film for a flexible wiring board (FPC board), a flexible copper-clad laminate, and the like. Substrate for board (FCCL substrate), heat-resistant insulating tape, wire enamel, semiconductor protective coating agent, liquid crystal alignment film, transparent conductive film for organic EL, TFT substrate for organic EL, color filter substrate, touch panel substrate, cover Glass substitute film, flexible substrate film, flexible transparent conductive film, transparent conductive film for organic thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, film for touch panel, seamless polyimide for copier Belt (so-called transfer belt), transparent electrode base (Transparent electrode substrate for organic EL, transparent electrode substrate for solar cell, transparent electrode substrate for electronic paper, etc.), interlayer insulating film, sensor substrate, image sensor substrate, light-emitting diode (LED) reflector (LED illumination reflector) : LED reflector), LED illumination cover, LED reflector illumination cover, coverlay film, high ductility composite substrate, resist for semiconductor, lithium ion battery, organic memory substrate, organic transistor substrate, organic semiconductor It can be suitably used suitably as a material used for applications such as a substrate, a color filter substrate, and a front film.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Characteristic evaluation method]
First, the evaluation method of the characteristic of the compound and polymer obtained in the Example etc. which are shown below is demonstrated.

<Identification of molecular structure>
For identification of the molecular structure of the compound obtained in each example or each comparative example, measurements such as infrared absorption spectrum measurement (IR measurement) and nuclear magnetic resonance spectrum measurement (NMR measurement) are appropriately employed depending on the compound. It was done by doing. In addition, for IR measurement and NMR measurement, an IR measuring device (FT / IR-4100 manufactured by JASCO Corporation) and an NMR measuring device (manufactured by VARIAN, trade name: UNITY INOVA-600) are used as measuring devices, respectively. It was.

<Measurement of total light transmittance, haze (turbidity) and yellowness (YI)>
Samples for measuring the total light transmittance (unit:%), haze (turbidity: HAZE), and yellowness (YI) of polyimide as measured in each example etc. (polyimide in film shape) By using the product name “Hazemeter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. or the product name “spectral colorimeter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. Asked. The total light transmittance and haze are measured with a trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd., and the yellowness is measured with a product name “Spectral Color Meter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. It was measured. Further, the total light transmittance is obtained by performing measurement in accordance with JIS K7361-1 (issued in 1997), and the haze (turbidity) is obtained by performing measurement in accordance with JIS K7136 (issued in 2000). The chromaticity (YI) was determined by performing measurement in accordance with ASTM E313-05 (issued in 2005).

<Measurement of linear expansion coefficient (CTE)>
The linear expansion coefficient (CTE) of polyimide is a measurement sample by forming a film having a size of 20 mm in length, 5 mm in width, and 13 μm in thickness from the polyimide (film-shaped polyimide) obtained in each example etc. Using a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku), adopting a tension mode (49 mN) and a heating rate of 5 ° C./min under a nitrogen atmosphere, 50 ° C. to 200 ° C. The change in the length of the sample was measured, and the average value of the change in length per 1 ° C. in the temperature range of 50 ° C. to 200 ° C. was measured.

<Measurement of 5% weight loss temperature (Td 5%)>
The 5% weight reduction temperature of polyimide was prepared by preparing 2 to 4 mg samples from the polyimides obtained in each Example, etc., and placing them in an aluminum sample pan. A thermogravimetric analyzer (SII Using a trade name “TG / DTA220” manufactured by Nanotechnology Co., Ltd.), setting the scanning temperature from 30 ° C. to 550 ° C. in a nitrogen gas atmosphere, heating at a temperature rising rate of 10 ° C./min, It was determined by measuring the temperature at which the weight of the sample used was reduced by 5%.

Example 1
<Step of producing tetracarboxylic acid ester compound>
In a container of 1000 mL glass autoclave (trade name “Hyperblaster TEM-V type” manufactured by pressure-resistant glass industry), methanol (820 mL), CuCl ₂ (II) (81.6 g, 454 mmol), the following general formula (I ):

5-norbornene-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -5 ″ -norbornene (35.6 g, 148 mmol: hereinafter sometimes referred to as “raw material compound”. ) And Pd ₃ (OAc) ₅ (NO ₂ ) (166 mg, 0.74 mmol in terms of Pd) were added to obtain a mixed solution. Pd ₃ (OAc) ₅ (NO ₂ ) was produced by employing the method described on page 1991 of Dalton Trans (vol. 11) issued in 2005. Further, the norbornene compound represented by the above general formula (I) was produced by adopting the same method as disclosed in Synthesis Example 1 of International Publication No. 2011/099518.

  Subsequently, the glass tube was arrange | positioned so that gas could be bubbled through the glass tube with respect to the liquid mixture which exists in the inside of the said container. Then, the said container was sealed and internal atmospheric gas was substituted with nitrogen. Thereafter, a vacuum pump was connected to the container to reduce the pressure in the container (pressure in the container: 0.015 MPa). Next, while supplying carbon monoxide through the glass tube at a rate (flow rate) of 0.015 molar equivalent / minute with respect to the raw material compound, the temperature is adjusted to 25 to 30 ° C. While maintaining the pressure in the container at 0.13 MPa, the mixture was stirred for 5 hours, and then the pressure in the container was further reduced to 0.13 MPa under the condition of temperature: 40 ° C. The mixture was stirred for 3 hours so as to maintain the reaction solution. Next, the atmosphere gas containing carbon monoxide is removed from the inside of the container, and the reaction solution is concentrated with an evaporator to remove (evaporate) methanol from the reaction solution, thereby producing a tetracarboxylic acid ester compound (reaction product). Product) (yield 65.4 g, yield 92.6%, polymer 2.20%: the yield and yield were determined by high performance liquid chromatography (HPLC, Agilent) Manufactured, 1200 series) values obtained by measurement by analysis, and the ratio of the polymer is a value obtained by measurement by GPC analysis.

<Filtration process>
After the crude product of the tetracarboxylic acid ester compound was transferred to another container (glass container with a capacity of 2000 mL), toluene (1200 mL) was added to the crude product at a temperature of 80 ° C. By vigorously stirring for 1 hour, the tetracarboxylic acid ester compound was extracted with toluene to obtain a toluene extract (concentration of the product: 8.4% by mass). Next, while maintaining the temperature of the toluene extract at 80 ° C., the Kiriyama funnel is used to separate CuCl and Pd ₃ (OAc) ₅ (NO ₂ ), which are components not dissolved in toluene, from the toluene extract. The reduced-pressure filtration used was performed and the toluene extract (filtrate) after filtration was obtained.

<Washing process>
Next, the toluene extract (filtrate) obtained after the filtration step was washed three times with 5% by mass hydrochloric acid (200 ml) under the temperature condition of 80 ° C. Subsequently, the toluene extract thus washed with hydrochloric acid was washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 ml) under the temperature condition of 80 ° C. Next, the toluene extract thus washed with a saturated aqueous solution of sodium hydrogen carbonate was washed twice with ion-exchanged water (200 ml) under the temperature condition of 80 ° C., and the obtained toluene extract was filtered with a filter. By filtration, a toluene extract after washing (concentration of reaction product: 7.9% by mass) was obtained.

<Toluene removal process>
The toluene extract obtained after the washing step (concentration of reaction product: 7.9% by mass) was concentrated by heating to about 110 ° C., which is the boiling point of toluene, at normal pressure (0.1 MPa). By such a concentration operation, 900 ml of toluene in a total amount was distilled off to obtain a concentrated solution (concentrated solution of the toluene extract) in which the concentration of the reaction product was adjusted to 25% by mass. Thereafter, the concentrated solution was allowed to cool at room temperature (25 ° C.) for about 12 hours to precipitate white crystals. Next, white crystals were filtered off from the concentrated solution. Thereafter, the filtered white crystals were washed twice with 50 mL of toluene. The white crystals thus obtained were subjected to a vacuum drying step at 60 ° C. to evaporate toluene adhering to the crystals to obtain solids (white crystals, 33.9 g, yield 48). %).

<Acetic acid recrystallization process (purification process)>
Next, 135.9 g of acetic acid was added so that the concentration of the obtained solid content (white crystals) was 20% by mass, and the crystals were dissolved by heating to about 110 ° C. Then, the solution was dissolved at room temperature ( The white crystals were precipitated by allowing to cool at 25 ° C. for about 12 hours to obtain a solution containing the white crystals. Next, white crystals are filtered off from the solution, washed twice with 50 mL of toluene, and the obtained white crystals are subjected to a vacuum drying process at 60 ° C. Was evaporated to obtain a tetracarboxylic acid ester compound (white crystals, 29.7 g, yield 42%).

In order to confirm the structure of the product (tetracarboxylic acid ester compound) thus obtained, IR measurement and NMR ( ¹ H-NMR) measurement were performed. The following general formula (II):

(Norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic acid tetramethyl ester) confirmed. Further, when GPC analysis was performed on the product thus obtained, a polymer which is an impurity (a polymer obtained by addition polymerization of a norbornene ring in the raw material compound or a plurality of norbornene rings having a keto group). The content of the combined polymer mixture etc.) was 0.27%. The obtained product was dissolved in N, N-dimethylacetamide to prepare a 5 mass% solution, and a UV-Vis measuring device (trade name “UV-2550”) manufactured by Shimadzu Corporation was used as a measuring device. As a result, the transmittance of 400 nm light was measured, and the transmittance of 400 nm light was 99.4%.

<Production process of acid dianhydride>
In a flask with a reflux tube having a capacity of 300 mL, 10 g of a tetracarboxylic acid ester compound (compound represented by the above general formula (II)) obtained after the acetic acid recrystallization step (purification step) is dissolved in 190 g of acetic acid. Then, 0.38 g of tetrafluoroethanesulfonic acid (HCF ₂ CF ₂ SO ₃ H, boiling point: 210 ° C.) was added as a homogeneous acid catalyst to the solution. Next, after replacing the atmosphere gas in the flask with nitrogen, the solution was heated with stirring using a magnetic stirrer under a nitrogen stream under atmospheric pressure. By such heating, the temperature in the flask was set to 118 ° C., and refluxing was performed for 0.5 hours (refluxing step). After such a reflux step, vapor generated using a Liebig condenser is heated under a heating condition of 118 ° C., and at the same time, acetic acid is added into the flask using a dropping funnel so that the liquid volume in the flask becomes constant. (Hereinafter referred to as “step (i)”). In addition, in such step (i), a white precipitate is generated in the liquid (reaction solution) in the flask after 2 hours have elapsed after the start of evaporation of the vapor. confirmed. In step (i), the distillate distilled off from the system was analyzed by mass measurement and gas chromatography every hour to confirm the degree of progress of the reaction. Such an analysis confirmed that acetic acid, methyl acetate, and water were present in the distillate. Moreover, when the removal speed | rate of the distillate in the above processes was measured, the speed | rate (ratio) by which a distillate was removed was about 35 mL per hour. And after starting distillation of vapor | steam in such a process (i), since distillation of methyl acetate stopped after 4 hours passed, heating was stopped and the said process (i) was complete | finished. In addition, the distillation amount (total amount) of methyl acetate from the start of distillation until 4 hours later was 5.5 g. The amount of acetic acid distilled off until the distillation of methyl acetate stopped (until the reaction was completed) was 85 g.

  Thus, after performing step (i), acetic acid is distilled off from the solution in the flask to obtain a concentrated solution, and then the concentrated solution is filtered under reduced pressure using a filter paper to obtain a white solid. Got the minute. The resulting white solid was washed 5 times with ethyl acetate (10 mL) (ethyl acetate washing step). Thereafter, the solid content after the ethyl acetate washing step was dried at 80 ° C. for 24 hours to obtain 7.6 g of white powder.

  A part of the powder thus obtained was collected and analyzed by high performance liquid chromatography (HPLC, 1200 series, manufactured by Agilent). As a result, the obtained white powder gives a single peak. (A single product was obtained). From the results of the liquid chromatographic analysis, no residual raw material compound (the tetracarboxylic acid ester compound) was confirmed. Moreover, when NMR measurement was performed in order to identify the structure of the crystalline compound thus obtained, the obtained compound had the following general formula (III):

It was confirmed that it is tetracarboxylic dianhydride (CpODA) represented by.

  Next, using the obtained tetracarboxylic dianhydride (CpODA), the contents of copper (Cu), palladium (Pd) and boron (B) contained in the compound (CpODA) are as follows. Measured (analyzed). That is, first, 0.2 g of tetracarboxylic dianhydride (CpODA) in a Teflon (registered trademark) container for a microwave decomposing apparatus, a 96 mass% ultra high purity sulfuric acid aqueous solution (1 mL: trade name “manufactured by Kanto Chemical Co., Ltd.” Ultra high purity reagent ultra pure sulfuric acid ") and 60% by mass ultra high purity perchloric acid aqueous solution (2mL: trade name" Ultra high purity reagent ultra pure perchloric acid (60%) "manufactured by Kanto Chemical Co., Inc.)) The container was placed in a microwave decomposition apparatus (trade name “MultiWave 3000” manufactured by PerkinElmer). Next, in such a microwave decomposition apparatus, after holding at an output of 800 W for 20 minutes, holding at an output of 1400 W for 20 minutes, a tetracarboxylic acid dihydrate is mixed in a mixed solution of an ultrahigh purity sulfuric acid aqueous solution and an ultrahigh purity perchloric acid aqueous solution. After dissolving the anhydride (CpODA), the solution is diluted with ultrapure water (trade name “Ultrapure Reagent Ultrapure Ultrapure Water” manufactured by Kanto Chemical Co., Ltd.) to a total volume of 50 mL. Prepared. Using the solution (sample) thus obtained, analysis is performed with an ICP emission spectrometer (trade name “iCap630 Duo” manufactured by Thermo Fisher Co., Ltd.) under conditions of axial photometry (axial) and measurement time of 30 seconds. Then, the contents of copper (Cu), palladium (Pd) and boron (B) contained in the compound (tetracarboxylic dianhydride: CpODA) were measured (analyzed). As a result of such measurement, in the obtained tetracarboxylic dianhydride (CpODA), the Cu content is less than 0.2 ppm (<0.2 ppm: a value smaller than the detection limit value), and the Pd content The amount was less than 0.2 ppm (<0.2 ppm: a value smaller than the detection limit value), and the B content was confirmed to be 0.3 ppm.

(Examples 2-4 and Comparative Examples 1-2)
By appropriately changing the washing step and the acetic acid recrystallization step (purification step) performed on the tetracarboxylic acid ester compound and the ethyl acetate washing step performed in the acid dianhydride manufacturing step, the metal component (copper (Cu ), Palladium (Pd) and boron (B)), the tetracarboxylic dianhydrides (CpODA) represented by the above general formula (III) having the amounts shown in Table 1 were obtained. In addition, the content of copper (Cu), palladium (Pd), and boron (B) shown in Table 1 is a value measured by adopting the same method as that employed in Example 1.

(Example 5)
<Preparation process of polyamic acid>
First, a 30 ml three-necked flask was heated with a heat gun and sufficiently dried. Next, the atmosphere gas in the three-necked flask that was sufficiently dried was replaced with nitrogen, and the inside of the three-necked flask was changed to a nitrogen atmosphere. Next, the following general formula (IV):

After adding 0.2045 g (0.90 mmol: Nippon Pure Chemical Industries, Ltd .: DABAN), which is an aromatic diamine represented by the following formula, 2.7 g of N, N-dimethylacetamide is added. By stirring, aromatic diamine (DABAN) was dissolved in the N, N-dimethylacetamide to obtain a solution.

  Next, in a three-necked flask containing the dissolution solution, under a nitrogen atmosphere, tetracarboxylic dianhydride obtained in Example 1 (CpODA: Cu content: less than 0.2 ppm (<0.2 ppm), After adding 0.3459 g (0.90 mmol) of Pd content: less than 0.2 ppm (<0.2 ppm) and B content: 0.3 ppm), at room temperature (25 ° C.) for 12 hours under nitrogen atmosphere By stirring, tetracarboxylic dianhydride (CpODA) and the aromatic diamine (DABAN) were reacted to form a polyamic acid to obtain a reaction liquid (polyamic acid solution).

  In addition, the intrinsic viscosity [η] of the polyamic acid formed in this manner was measured using an automatic viscosity measuring apparatus (trade name “VMC-252”) manufactured by Koiso Co., Ltd., with N, N-dimethylacetamide as a solvent and a concentration. A measurement sample (polyamic acid solution) of 0.5 g / dL of polyamic acid was prepared and measured under a temperature condition of 30 ° C. That is, using part of the polyamic acid solution (the reaction solution [solvent: N, N-dimethylacetamide]), an N, N-dimethylacetamide solution having a polyamic acid concentration of 0.5 g / dL is prepared. Then, when the intrinsic viscosity [η] of the polyamic acid was measured under the above conditions, the intrinsic viscosity [η] of the polyamic acid was 0.90 dL / g.

<Polyimide preparation process (imidization process)>
A non-alkali glass (trade name “Eagle XG” manufactured by Corning Inc., length: 100 mm, width 100 mm, thickness 0.7 mm) was prepared as a glass substrate, and the reaction solution (polyamic acid solution) obtained as described above was prepared. Was spin-coated on the surface of the glass substrate so that the thickness of the coating film after heat curing was 13 μm, thereby forming a coating film on the glass substrate. Thereafter, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ° C. and allowed to stand for 2 hours, and the solvent was evaporated and removed from the coating film (solvent removal treatment).

  After such solvent removal treatment, the glass substrate on which the coating film has been formed is put into an inert oven in which nitrogen is flowing at a flow rate of 3 L / min, and in the inert oven at 25 ° C. under a nitrogen atmosphere. After standing for 0.5 hour, heated at 135 ° C. for 0.5 hour, further heated at 380 ° C. for 1 hour to cure the coating film, and made of polyimide on the glass substrate A film was formed.

Thus, IR analysis was performed with respect to the film which consists of a polyimide obtained by using IR measuring machine (JASCO Corporation FT / IR-4100). The IR analysis results (IR spectrum graph) thus obtained are shown in FIG. As is clear from the results shown in FIG. 1, since the C═O stretching vibration of imidecarbonyl was observed at 1698 cm ⁻¹ , it was confirmed that the film was a film made of polyimide. Moreover, the polyimide obtained from the kind of monomer used is a polymer of the tetracarboxylic dianhydride (CpODA) and the aromatic diamine (DABAN), and is represented by the general formula (2). [Wherein, R ¹ , R ² , R ³ in the formula are all hydrogen atoms, and R ⁴ is a group represented by the above general formula (8) (wherein Q is —CONH -. It was found to contain the The properties of the obtained polyimide are shown in Table 2.

(Example 6)
Instead of the tetracarboxylic dianhydride obtained in Example 1, the tetracarboxylic dianhydride obtained in Example 2 (CpODA: Cu content: less than 0.2 ppm (<0.2 ppm), Pd A film made of polyimide was formed in the same manner as in Example 5, except that the content of 2.2 ppm and the content of B: 0.3 ppm were used.

(Example 7)
Instead of the tetracarboxylic dianhydride obtained in Example 1, the tetracarboxylic dianhydride obtained in Example 3 (CpODA: Cu content: less than 0.2 ppm (<0.2 ppm), Pd A polyimide film was formed in the same manner as in Example 5, except that the content of 11 ppm and the content of B: 3.7 ppm were used.

(Example 8)
Instead of the tetracarboxylic dianhydride obtained in Example 1, the tetracarboxylic dianhydride obtained in Example 4 (CpODA: Cu content: less than 0.2 ppm (<0.2 ppm), Pd A polyimide film was formed in the same manner as in Example 5 except that the content of 1.5 ppm and the content of B: 5.1 ppm were used.

(Comparative Example 3)
Instead of the tetracarboxylic dianhydride obtained in Example 1, the tetracarboxylic dianhydride obtained in Comparative Example 1 (CpODA: Cu content: 12 ppm, Pd content: 0.2 ppm, B A film made of polyimide was formed in the same manner as in Example 5 except that the content of 0.8 ppm was used.

(Comparative Example 4)
Instead of the tetracarboxylic dianhydride obtained in Example 1, the tetracarboxylic dianhydride obtained in Comparative Example 2 (CpODA: Cu content: 19 ppm, Pd content: 2.0 ppm, B A film made of polyimide was formed in the same manner as in Example 5 except that the content of 3.7 ppm was used.

  As is apparent from the results shown in Tables 1 and 2, when a polyimide is produced using the tetracarboxylic dianhydride (Examples 1 to 4) of the present invention in which the Cu content is less than 0.2 ppm ( In all of Examples 5 to 8, the 5% weight loss temperature (Td5%) was 494 ° C. or higher, and it was confirmed that the heat resistance with Td5% as an index was very high. . On the other hand, in the case of producing a polyimide using a tetracarboxylic dianhydride (Comparative Examples 1 to 2) having a Cu content of 12 ppm or more (Comparative Examples 3 to 4), 5% by weight The decrease temperatures (Td 5%) were all 490 ° C. or lower. From these results, there is a correlation between the Cu content and the heat resistance with Td of 5% as an index, and the copper (Cu) content in the tetracarboxylic dianhydride is set to a lower value. Thus, it was found that a higher degree of heat resistance can be obtained when polyimide is formed.

  Moreover, from the results shown in Tables 1 and 2, for example, polyimides obtained using tetracarboxylic dianhydrides (Examples 1 to 4) having a Cu content of less than 0.2 ppm (Examples 5 to 5). When the results of 8) are compared, when the tetracarboxylic dianhydride (CpODA) obtained in Examples 1-2 and Example 4 in which the content of palladium (Pd) is 2.2 ppm or less is used In Examples 5-6 and 8, the yellowness (YI) of the resulting polyimide is 3.5 or less and the total light transmittance is 87.1% or more, whereas palladium (Pd ) Content of 11 ppm, when the tetracarboxylic dianhydride (CpODA) obtained in Example 3 was used (Example 7), the yellowness (YI) of the polyimide obtained was the above value. (3.5) and higher than Total light transmittance was lower than the value (87.1%). From such results, by using tetracarboxylic dianhydride (CpODA) with a lower content of copper (Cu) and a lower content of palladium (Pd), Td 5% can be reduced. It has been found that it is possible to produce a polyimide having a higher level of transparency while achieving higher heat resistance as an index.

  Moreover, when the result of the polyimide (Examples 5-8) obtained using the tetracarboxylic dianhydride (Examples 1-4) whose Cu content is less than 0.2 ppm is compared, the tetracarboxylic acid dianhydrides are compared. The boron content in the anhydride is increased in the order of “Examples 1 and 2 <Example 3 <Example 4”, but the tetra content obtained in Examples 1 and 2 having a lower boron content. In the case of using carboxylic dianhydride (Examples 5 to 6), it was found that Td5% was a very high value of 502 ° C. or higher, and a higher level of heat resistance was achieved. It was. From such a result, it is higher by using tetracarboxylic dianhydride (CpODA) in which the content of copper (Cu) is lower and the content of boron (B) is lower. It was also found that a level of heat resistance was obtained.

  As described above, according to the present invention, a tetracarboxylic dianhydride that makes it possible to more reliably produce a polyimide having a sufficiently high level of heat resistance, and a sufficiently high level of heat resistance. It becomes possible to provide the polyimide which has, and the manufacturing method of the polyimide.

  Accordingly, the tetracarboxylic dianhydride of the present invention is particularly suitable for polyimides for flexible wiring boards, polyimides for heat-resistant insulating tapes, polyimides for electric wire enamel, polyimides for protective coatings of semiconductors, liquid crystals that require heat resistance. Polyimide for alignment film, polyimide for organic EL transparent electrode substrate, polyimide for solar cell transparent electrode substrate, polyimide for electronic paper transparent electrode substrate, various gas barrier film substrate materials, polyimide for interlayer insulation film, It is useful as a raw material compound for producing polyimide for sensor substrates, polyimide for printer transfer belts, and the like.

Claims (5)

The following general formula (1):
[In the formula (1), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom; An integer of 12 is shown. ]
And a compound represented by
A tetracarboxylic dianhydride, characterized in that the Cu content is 10 ppm or less.   The tetracarboxylic dianhydride according to claim 1, wherein the content of Pd is 10 ppm or less.   The tetracarboxylic dianhydride according to claim 1 or 2, wherein the content of B is 5 ppm or less. The tetracarboxylic dianhydride according to any one of claims 1 to 3, and the following general formula (3):
_{^{H 2 N-R 10 -NH 2}} (3)
[In the formula (3), R ¹⁰ represents an aryl group having 6 to 50 carbon atoms. ]
And a polymer with an aromatic diamine represented by the following general formula (2):
[In the formula (2), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R ¹⁰ represents carbon. An aryl group having a number of 6 to 50 is shown, and n is an integer of 0 to 12. ]
The polyimide of the description characterized by containing the repeating unit represented by these. The tetracarboxylic dianhydride according to any one of claims 1 to 3, and the following general formula (3):
_{^{H 2 N-R 10 -NH 2}} (3)
[In the formula (3), R ¹⁰ represents an aryl group having 6 to 50 carbon atoms. ]
After forming a polyamic acid by reacting with an aromatic diamine represented by the following, by imidizing the polyamic acid,
It is a polymer of the tetracarboxylic dianhydride and the aromatic diamine, and the following general formula (2):
Wherein ^{(2), R 1, R} 2, R 3 are each independently a hydrogen atom, it represents one selected from the group consisting of alkyl groups and fluorine atom having 1 to 10 carbon ^{atoms, R 10} is A C6-C50 aryl group is shown, n shows the integer of 0-12. ]
Obtaining a polyimide containing a repeating unit represented by:
A method for producing polyimide, characterized by the following.