TW202304871A - Tetracarboxylic dianhydride, carbonyl compound, acid-anhydride-group-containing compound, methods for producing these, polyimide, and polyimide precursor resin - Google Patents

Abstract

Provided is a tetracarboxylic dianhydride represented by general formula (1): [in formula (1), R1-R5 each independently represent one selected from the group consisting of hydrogen atoms and C1-20 hydrocarbon groups].

Description

Tetracarboxylic dianhydride, carbonyl compound, acid anhydride group-containing compound, production method thereof, polyimide and polyimide precursor resin

The present invention relates to a method for producing tetracarboxylic dianhydride, carbonyl compound, compound containing acid anhydride group and the like, polyimide and polyimide precursor resin.

Generally speaking, tetracarboxylic dianhydrides are used in the fields of raw materials for producing polyimides, epoxy hardeners, and pharmaceutical intermediates. Moreover, various compounds (aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, etc.) have been conventionally known as such tetracarboxylic dianhydride. Also, polyimides have been attracting attention as a material having high heat resistance, light weight, and flexibility, and various polyimides have been studied.

For example, Japanese Patent Application Laid-Open No. 2015-7219 (Patent Document 1) discloses pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,6, Aromatic tetracarboxylic dianhydrides such as 7-naphthalene tetracarboxylic dianhydride, and discloses an aromatic polyimide (aromatic polyimide) having the above-mentioned aromatic tetracarboxylic dianhydride A repeating unit obtained by reacting with a specific aromatic diamine compound. However, when the conventional aromatic tetracarboxylic dianhydride described in Patent Document 1 is used to produce polyimide, although polyimide with high heat resistance can be obtained, the yellowness (YI) is low. The value becomes large and brown. Moreover, the conventional aromatic tetracarboxylic dianhydride described in patent document 1 is also difficult to manufacture the polyimide which the value of haze (HAZE) is low. Therefore, for example, it is difficult to apply polyimide obtained by using an aromatic tetracarboxylic dianhydride to applications requiring transparency. Thus, when the previous aromatic tetracarboxylic dianhydrides were used to manufacture polyimides, yellowness (YI) and turbidity (HAZE) were both below a certain level (for example, YI was 20 or less and HAZE 15 or less) and other problems (that is, the conventional aromatic polyimides have both yellowness (YI) and turbidity (HAZE) below a certain level (for example, YI is 20 or less and HAZE is 15 or less), etc. problems exist).

In addition, International Publication No. 2017/98936 (Patent Document 2) discloses cyclohexanetetracarboxylic dianhydride, 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic acid-3 ,4: 3', 4'-dianhydride, cyclobutane tetracarboxylic dianhydride and other alicyclic tetracarboxylic dianhydrides, and discloses the amide of the above-mentioned alicyclic tetracarboxylic dianhydride and aromatic diamine The amine is polyimide (alicyclic polyimide). When the conventional alicyclic tetracarboxylic dianhydride described in this patent document 2 is used as a raw material for polyimide, although it is possible to produce a polyimide whose coloring is suppressed, the obtained polyimide The heat resistance of imide is low, so it cannot be used in applications requiring heat resistance. Thus, conventional alicyclic tetracarboxylic dianhydrides have problems in heat resistance when polyimides are produced using them (that is, conventional alicyclic polyimides have problems in heat resistance).

And, in order to eliminate the problems of such aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and previous polyimides, in recent years, when used in the manufacture of polyimides, From the viewpoint of ensuring sufficient transparency, etc., a tetracarboxylic dianhydride with a new structure has been developed, which can keep the yellowness and turbidity below a certain level (specific reference value) and at the same time can make the heat resistance high.

For example, International Publication No. 2015/163314 (Patent Document 3) discloses a tetracarboxylic dianhydride represented by a specific general formula having a noralkane ring and an aromatic ring in the skeleton structure, and discloses a tetracarboxylic dianhydride based on the above four Polyimide obtained from carboxylic dianhydride and aromatic diamine as raw materials. When the tetracarboxylic dianhydride described in this patent document 3 is used as a raw material of polyimide, heat resistance can be obtained while keeping yellowness (YI) and haze (HAZE) below a certain level. Higher polyimide. Furthermore, according to different uses, the characteristics of special requirements, etc. are also different. Therefore, in the field of polyimide, it is expected that a part of the characteristics can be made more excellent when polyimide is formed (for example, it can make A novel tetracarboxylic dianhydride and a novel polyimide whose yellowness and turbidity are below a certain level and which have some properties better than those of the polyimide described in Patent Document 3). prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2015-7219 Patent Document 2: International Publication No. 2017/98936 Patent Document 3: International Publication No. 2015/163314

[Problem to be solved by the invention]

The present invention is made in view of the problems of the above-mentioned prior art, and its object is to provide a method that can improve the yellowness and Tetracarboxylic dianhydrides whose turbidity is lower than a certain level and which can improve heat resistance; carbonyl compounds that can be used as raw materials for efficiently producing the tetracarboxylic dianhydrides; An acid anhydride group-containing compound obtainable as an intermediate of the above-mentioned tetracarboxylic dianhydride; a production method capable of efficiently and reliably producing the above-mentioned tetracarboxylic dianhydride; and a compound capable of efficiently and reliably producing the above-mentioned carbonyl compound Manufacturing method. Also, the object of the present invention is to provide a polyimide that can make the yellowness and turbidity lower than a certain level and can make the heat resistance higher, and can be preferably used in the production of the polyimide. Polyimide precursor resin of imide. [Technical means to solve the problem]

The inventors of the present invention have repeatedly conducted intensive research in order to achieve the above object, and as a result found that by making the tetracarboxylic dianhydride a compound represented by the following general formula (1), it is surprising that when it is used as In the case of the raw material monomers for the manufacture of polyimides, the yellowness and turbidity of the obtained polyimides can be lowered below a certain level (letting YI be the previous aromatic tetracarboxylic acid A value of 20 or less that cannot be achieved by dianhydrides, while making HAZE a value of 15 or less), can also be achieved compared to the case of using tetracarboxylic dianhydrides described in the above-mentioned patent document 3 to produce polyimides. Higher heat resistance can make the heat resistance of polyimide at a higher level, and it is also found that the compound represented by the following general formula (1) and the tetracarboxylic acid described in the above-mentioned patent document 3 Compared with the case of producing polyimide with dianhydride, the coefficient of linear expansion can be lowered, and the present invention has been completed.

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

[chemical 1]

[In formula (1), R ¹ to R ⁵ each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons] Furthermore, the compounds represented by the general formula (1) include The tetracarboxylic dianhydride of the present invention has two carboxylic anhydride groups, but the structure of the part of the skeleton to which each carboxylic anhydride group is bonded (one of which is bonded to the noralkane skeleton, and the other is bonded to the benzene skeleton Bonding) is very different, therefore, the reactivity of each carboxylic acid anhydride group in a compound is very different, so it can also be preferably applied to the design of chemoselective polymerization reactions, etc.

The carbonyl compound of the present invention is represented by the following general formula (2):

[Chem 2]

[In formula (2), R ¹ to R ⁵ independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁶ and R ⁷ independently represent a group selected from a hydrogen atom and one of the group consisting of hydrocarbon groups with 1 to 10 carbon atoms].

Also, the compound containing acid anhydride group of the present invention is represented by the following general formula (3):

[Chem 3]

[In formula (3), R ¹ to R ⁵ independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁶ independently represent a group selected from a hydrogen atom and a carbon number One of the group consisting of 1 to 10 hydrocarbon groups].

Also, the manufacturing method of the tetracarboxylic dianhydride of the present invention is to obtain the above-mentioned general formula ( 1) The method of tetracarboxylic dianhydride represented.

Also, the production method of the carbonyl compound of the present invention is to make the following general A method for obtaining a carbonyl compound represented by the above-mentioned general formula (2) by reacting an aromatic compound represented by the formula (4) with an alicyclic compound represented by the following general formula (5).

[chemical 4]

[In formula (4), R ¹ to R ³ independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons, and R ⁶ independently represent one selected from the group consisting of 1 to 10 carbons. One of the group consisting of hydrocarbon groups, X represents a halogen atom]

[chemical 5]

[In formula (5), R ⁴ to R ⁵ independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁷ independently represent one selected from the group consisting of 1 to 10 carbons One of the group consisting of hydrocarbon groups].

Also, the present inventors found that by making polyimide a monomer containing at least one compound selected from the group consisting of tetracarboxylic dianhydride represented by the above general formula (1) and derivatives thereof Surprisingly, the polycondensate of (A) and the monomer (B) as a diamine compound can make the yellowness and turbidity of the obtained polyimide all be lower than a certain level (making YI is a value of 20 or less, which cannot be achieved by conventional aromatic tetracarboxylic dianhydrides, and HAZE is a value of 15 or less), and compared with the polyimide described in the above-mentioned patent document 3, it can also be achieved. Higher heat resistance can make the heat resistance of polyimide at a higher level, and it is also found that by using polyimide containing the above-mentioned polycondensate, and using the tetracarboxylic dianhydride described in the above-mentioned patent document 3 Compared with the case of producing polyimide, the coefficient of linear expansion can be lowered, and the present invention has been completed.

That is, the polyimide of the present invention contains a polycondensate of a monomer (A) and a monomer (B) as a diamine compound, and the monomer (A) contains tetracarboxylic At least one compound of the group consisting of acid dianhydride and its derivatives.

Furthermore, the polyamic acid of the present invention contains a polyadduct of a monomer (A) and a monomer (B) as a diamine compound. At least one compound of the group consisting of tetracarboxylic dianhydride and its derivatives. [Effect of Invention]

According to the present invention, when used as a raw material monomer for producing polyimide, the yellowness and turbidity of the polyimide obtained can be lower than a certain level, and Tetracarboxylic dianhydride capable of improving heat resistance; carbonyl compound that can be used as a raw material for efficiently producing the tetracarboxylic dianhydride; available as an intermediate of the above-mentioned tetracarboxylic dianhydride The obtained compound containing an acid anhydride group; the production method capable of efficiently and reliably producing the above-mentioned tetracarboxylic dianhydride; and the production method capable of efficiently and reliably producing the above-mentioned carbonyl compound. Also, according to the present invention, it is possible to provide a polyimide that can make both the yellowness and the turbidity lower than a certain level and that can make the heat resistance higher, and can be preferably used in the production of the polyimide. Polyimide precursor resin of imide.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof. In addition, in this specification, unless otherwise specified, the expression "X~Y" regarding numerical values X and Y means "above X and below Y". Where in the expression only the value Y is marked with a unit, that unit may also be applied to the value X.

[Tetracarboxylic dianhydride] The tetracarboxylic dianhydride of the present invention is represented by the above general formula (1). Furthermore, R ¹ to R ⁵ in the general formula (1) each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.

The hydrocarbon groups of R ¹ to R ⁵ in the above general formula (1) can be selected as long as they have 1 to 20 carbons (more preferably 1 to 10, more preferably 1 to 5, especially preferably 1 to 3) Can. When the number of carbons is set to be below the above-mentioned upper limit, compared with the case of exceeding the above-mentioned upper limit, the temperature of the reflow condition at the time of production can be lowered, thereby reducing side reactions such as decomposition during production, and improving transparency. Compared with the case of using the obtained tetracarboxylic dianhydride to form polyimide, it is higher (the transparency of the formed polyimide can be further improved), and the obtained tetracarboxylic acid dianhydride can be further reduced. Amount of residual solvent contained in acid dianhydride. In addition, such a hydrocarbon group may be a saturated hydrocarbon group or may be an unsaturated hydrocarbon group. Furthermore, the above-mentioned hydrocarbon group may be linear, branched, or cyclic. Examples of such hydrocarbon groups include straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; branched-chain alkyl groups such as isopropyl and isobutyl; and cyclic alkyl groups such as cyclohexyl. ; Aromatic hydrocarbon groups such as benzyl, etc. Such hydrocarbon groups that may be R ¹ -R ⁵ in the general formula (1) are more preferably alkyl groups. Moreover, as such an alkyl group, a methyl group and an ethyl group are more preferable from the viewpoint of the easiness of purification.

In addition, R ¹ to R ⁵ in the above general formula (1) are preferably each independently a hydrogen atom, a methyl group, Ethyl, n-propyl or isopropyl, more preferably a hydrogen atom, methyl or ethyl, still more preferably a hydrogen atom or a methyl group, especially preferably a hydrogen atom.

Furthermore, the structure of this tetracarboxylic dianhydride can be determined by NMR (nuclear magnetic resonance, nuclear magnetic resonance) measurement.

In addition, the tetracarboxylic dianhydride of the present invention can be used in various applications depending on its structure, for example, it can be applied to monomers for polymer formation, epoxy curing agents, pharmaceutical raw materials, and the like. When the above-mentioned tetracarboxylic dianhydride is used as a monomer (polymer raw material) for polymer formation, for example, it can be preferably used to form polyamides such as polyimides, polyamides, and unsaturated polyesters. comonomers. Furthermore, when it is used for producing such a polymer, the operation at the time of polymerization is relatively easy due to the structure of the above-mentioned tetracarboxylic dianhydride. Also, when the above-mentioned tetracarboxylic dianhydride is used as a monomer for forming polyimide, for example, the above-mentioned tetracarboxylic dianhydride and diamine can be reacted in a solvent to prepare polyamic acid (polyamic acid), which is coated on a base material (such as a glass substrate, etc.) and fired to easily obtain a film-like polyimide. In addition, it does not specifically limit as such diamine, The well-known diamine used for polyimide manufacture can be used suitably. Furthermore, the polyimide obtained in this way can also have low yellowness and high heat resistance. Also, when used as an epoxy curing agent, it may be used as long as it is added to an epoxy, and the epoxy can be easily cured by heating (for example, heating at about 100 to 200° C.). Furthermore, since the reactivity of the acid anhydride group bonded to the aromatic part of the skeleton and the acid anhydride group bonded to the noralkane part of the skeleton is different, it can also cause a chemoselective reaction and can be used in the design of various products (for example, When designing various compounds as raw materials for pharmaceuticals, etc.).

[Carbonyl Compound] The carbonyl compound of the present invention is represented by the above general formula (2). Furthermore, R ¹ to R ⁵ in the general formula (2) each independently represent one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons, and R ⁶ and R ⁷ independently represent one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons. One of the group consisting of a free hydrogen atom and a hydrocarbon group with 1 to 10 carbon atoms.

R ¹ to R ⁵ in the general formula (2) have the same meaning as R ¹ to R ⁵ in the above general formula (1), preferably the same as R ¹ to R ⁵ in the above general formula (1).

In addition, the hydrocarbon groups that can be selected as R ⁶ and R ⁷ in the general formula (2) only need to have 1 to 10 carbons (more preferably 1 to 5, especially preferably 1 to 3). When such a carbon number is made below the said upper limit, synthesis|combination and purification can be made easy compared with the case of exceeding the said upper limit. In addition, such a hydrocarbon group may be a saturated hydrocarbon group or may be an unsaturated hydrocarbon group. Furthermore, the above-mentioned hydrocarbon group may be linear, branched, or cyclic. As such hydrocarbon groups that can be selected as ^R6 and ^R7 , for example, straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; branched-chain alkyl groups such as isopropyl and isobutyl; Cyclic alkyl groups such as cyclohexyl groups; Aromatic hydrocarbon groups such as benzyl groups, etc. Also, from the viewpoint of the ease of purification, the hydrocarbon groups that can be ^R6 and ^R7 in the general formula (2) are preferably alkyl groups, especially methyl groups and ethyl groups.

Also, from the viewpoint of ease of synthesis and purification, R ⁶ and R ⁷ in the general formula (2) are preferably each independently a hydrogen atom, a methyl group, an ethyl group, particularly preferably a methyl group, an ethyl group base. Furthermore, the structure of this carbonyl compound can be confirmed by NMR measurement.

[Acid Anhydride Group-Containing Compound] The acid anhydride group-containing compound of the present invention is represented by the above general formula (3). Furthermore, in the general formula (3), R ¹ to R ⁵ each independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons, and R ⁶ independently represent a group selected from a hydrogen atom and one of the group consisting of hydrocarbon groups with 1 to 10 carbon atoms.

R ¹ to R ⁵ in the general formula (3) have the same meaning as R ¹ to R ⁵ in the above general formula (1), preferably the same as R ¹ to R ⁵ in the above general formula (1). In addition, R ⁶ in the general formula (3) has the same meaning as the R ⁶ in the above general formula (2), preferably the same as R ⁶ in the above general formula (2). Furthermore, the structure of the compound containing an acid anhydride group can be confirmed by NMR measurement.

[Manufacturing method of tetracarboxylic dianhydride] The manufacture method of the tetracarboxylic dianhydride of the present invention is by using an acid catalyst (in the presence of an acid catalyst) to react the carbonyl compound represented by the above general formula (2) in a carboxylic acid with 1 to 5 carbon atoms A method of heating to obtain tetracarboxylic dianhydride represented by the above-mentioned general formula (1).

The carbonyl compound represented by the above-mentioned general formula (2) is the same as that described above as the carbonyl compound of the present invention, and the preferred ones are also the same.

As the above-mentioned acid catalyst, there is no particular limitation, and the reaction of making the ester group or the structural part of the carboxylic acid (the part of the diester or the dicarboxylic acid) bonded to two adjacent carbon atoms respectively to become an acid anhydride can be suitably used ( Hereinafter, it may be abbreviated as "acid anhydride reaction" as the case may be Or other known acid catalysts (such as hydrochloric acid, sulfuric acid, etc.)). Moreover, as such an acid catalyst, from the viewpoint of improving the reaction yield, trifluoromethanesulfonic acid and tetrafluoroethanesulfonic acid are more preferable, and trifluoromethanesulfonic acid is especially preferable. In addition, as such an acid catalyst, 1 type can be used individually, or 2 or more types can be used in combination.

Also, the amount of the acid catalyst used is not particularly limited, but it is preferably set as the mole amount of hydrogen ions (H ⁺ ) donated by the acid catalyst relative to 1 mole of the amount of the carbonyl compound used. The amount is 0.005-0.2 mol (more preferably 0.01-0.1 mol). If the amount of this acid catalyst used does not reach the above-mentioned lower limit, the reaction rate tends to decrease. On the other hand, when it exceeds the above-mentioned upper limit, it is difficult to further improve the effect obtained by using the catalyst, but the economic efficiency tends to decrease. . In addition, the concentration of the acid catalyst is preferably in the range of 0.50 to 5.0 mol% based on the total molar amount of the amount of the carbonyl compound used.

Moreover, in this invention, the carboxylic acid with 1-5 carbon atoms is used. Tetracarboxylic dianhydride can be efficiently produced by using such a C1-C5 carboxylic acid. Moreover, among such carboxylic acids having 1 to 5 carbon atoms, formic acid, acetic acid, and propionic acid are preferred, and acetic acid is more preferred from the viewpoint of easiness of production and purification. Such carboxylic acids may be used alone or in combination of two or more.

Also, in the present invention, the above-mentioned carbonyl compound is heated in the above-mentioned carboxylic acid with 1 to 5 carbons using the above-mentioned acid catalyst. In order to be able to heat in the carboxylic acid with 1-5 carbons, it is preferable to prepare the A mixture of carboxylic acid, the above-mentioned tetraester compound and the above-mentioned acid catalyst. The preparation method of such a mixture is not particularly limited, as long as it is prepared appropriately according to the equipment used in the heating step, for example, it can be prepared by adding (introducing) them into the same container.

In addition, when preparing such a mixture, another solvent may be further added to the above-mentioned carboxylic acid having 1 to 5 carbon atoms and used. As such other solvents, known ones that can be used in acid anhydride reactions (for example, solvents exemplified in paragraph [0146] of International Publication No. 2015/163314 (for example, ester solvents such as ethyl acetate, or Aromatic solvents such as benzene, toluene, etc.)).

Also, when the above-mentioned carbonyl compound is an ester compound (when R ^{and R} in the above-mentioned general formula (2) are both hydrocarbon groups), before adding the acid catalyst (before preparing the above-mentioned mixture), the The above-mentioned carbonyl compound is heated in a carboxylic acid with 1 to 5 carbons (or, as the case may be, in a mixture of a carboxylic acid with 1 to 5 carbons and other solvents), and ^R6 and ^R7 in the above carbonyl compound replaced by a hydrogen atom.

In addition, when using the above-mentioned acid catalyst to heat the above-mentioned carbonyl compound in the above-mentioned carboxylic acid having 1 to 5 carbon atoms (hereinafter, referred to as "heating step" for short as the case may be), it is preferable to distill the reaction The generated water and ester compounds of carboxylic acids with 1 to 5 carbon atoms (such as ethyl acetate, etc.) are discharged (removed) to the outside of the system, and the reaction proceeds. In addition, in the above-mentioned heating step, acetic anhydride may be used together with the above-mentioned carboxylic acid having 1 to 5 carbon atoms to remove water generated during the reaction. In addition, in the said heating process, it is preferable to employ|adopt the process of distilling water and the said ester compound from a viewpoint, such as further improvement of a yield. Moreover, it is preferable to make such a heating process into the process of distilling water and the said ester compound, making it reflux by heating.

Also, in the above-mentioned heating step, the heating temperature is preferably set at 80-180°C, more preferably at 80-150°C, further preferably at 100-140°C, and most preferably at 110-130°C. ℃. In addition, such heating temperature is preferably set to a temperature lower than the boiling point of the above-mentioned acid catalyst within the range of the above-mentioned temperature conditions. Moreover, heating time is not specifically limited, It is preferable to set it as 0.5-100 hours, and it is more preferable to set it as 1-50 hours. By setting the heating temperature and heating time so as to satisfy such conditions, the product can be obtained more efficiently.

Also, in the above-mentioned heating step, the pressure conditions (pressure conditions during the reaction) are not particularly limited, and can be under normal pressure, under increased pressure, or under reduced pressure. Both can be reacted, and when reflux is used, the reaction can be carried out under pressure conditions such as vapor of a carboxylic acid having 1 to 5 carbon atoms as a solvent. In addition, during the above-mentioned heating step, the atmosphere gas is not particularly limited, for example, it may be air or an inert gas (nitrogen, argon, etc.).

Furthermore, in the above-mentioned heating step, from the viewpoint of obtaining tetracarboxylic dianhydride with a higher yield, it is preferable that the concentration of the product in the above-mentioned mixture is 30 to 80% by mass (more preferably 40 to 60% by mass). ) to concentrate. When concentrating in this way and obtaining a concentrated solution, tetracarboxylic dianhydride can be obtained efficiently by cooling (for example, cooling to 20-30 degreeC) and crystallization (cooling crystallization).

By carrying out the said heating process in this way, the tetracarboxylic dianhydride represented by said general formula (1) can be obtained.

Furthermore, in the case of reflux in the above-mentioned heating step, in the case of directly carrying out reflux to proceed the reaction without extracting by-product water and ester compounds of carboxylic acids having 1 to 5 carbon atoms by distillation, or in When an acid anhydride is used in the heating step, the acid anhydride group-containing compound represented by the above general formula (3) can be produced simultaneously with the production of the tetracarboxylic dianhydride represented by the above general formula (1). In this way, the acid anhydride group-containing compound represented by the above-mentioned general formula (3) can be produced by appropriately changing the conditions employed in the above-mentioned heating step.

[Manufacturing method of carbonyl compound] The production method of the carbonyl compound of the present invention is by making the above general formula (4 ) reacts an aromatic compound represented by the above general formula (5) with an alicyclic compound represented by the above general formula (5) to obtain a carbonyl compound represented by the above general formula (2).

In the present invention, in order to obtain the carbonyl compound represented by the above general formula (2), the aromatic compound represented by the above general formula (4) is used. R ¹ to R ³ in the general formula (4) each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ to R ³ in this general formula (4) are respectively synonymous with R 1 to R ³ in the above general formula (2), and the preferred ones are also the same as ^{R 1 to} R ³ in the above general formula (2). same. In addition, R ⁶ in the above general formula (4) each independently represent one species selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. This kind can be R in the general formula (4) The hydrocarbyl group is respectively synonymous with the hydrocarbyl group that ^can be ^R in the above-mentioned general formula (2) The hydrocarbon groups of ^R6 are the same). Also, X in the above general formula (4) is a halogen atom. When X in the above general formula (4) is a halogen atom, a reductive Heck reaction can efficiently proceed between it and the alicyclic compound represented by the above general formula (5). Also, the halogen atom used as X in the above general formula (4) is more preferably a chlorine atom, a bromine atom, or an iodine atom, and particularly preferably a bromine atom or an iodine atom. Moreover, it does not specifically limit as such an aromatic compound, For example, dimethyl 4-bromophthalate, diethyl 4-bromophthalate, dimethyl 4-iodophthalate, 4-Iododiethylphthalate, etc. Moreover, the method for producing the aromatic compound represented by such general formula (4) is not specifically limited, A well-known method can be suitably used. In addition, as such an aromatic compound, what is marketed can be used suitably.

Moreover, in this invention, in order to obtain the carbonyl compound represented by the said general formula (2), the alicyclic compound represented by the said general formula (5) is used. R ⁴ to R ⁵ in the above general formula (5) each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons. R ⁴ to R ⁵ in this general formula (5) are respectively synonymous with R ⁴ to R ⁵ in the above general formula (2), and the preferred ones are also the same as R ⁴ to R ⁵ in the above general formula (2). same. R ⁷ in the above general formula (5) each independently represent one species selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. This kind can be R in the general formula (5) The hydrocarbyl group that can be R in the above-mentioned general formula (2) The hydrocarbyl group that can be ^respectively synonymous (it ^is better also can be the above-mentioned general formula (2) The hydrocarbyl group of ^R in is the same).

Examples of the alicyclic compound represented by the above general formula (5) include: 5-northene-2,3-dicarboxylic acid dimethyl Dimethyl diolate, dimethyl 5,6-dimethyl-dimethylate, etc. Also, the method for producing the alicyclic compound represented by the general formula (5) is not particularly limited, and known methods can be appropriately used. In addition, the alicyclic compound represented by the general formula (5) can be suitably used from commercially available products (for example, dimethyl benzoate etc. which can be used as the alicyclic compound represented by the above general formula (5) available commercially).

Also, as the reducing agent, at least one selected from the group consisting of formic acid, 2-propanol and hydrogen is used. By using such a reducing agent, the reductive Heck reaction can be efficiently performed, and the target product can be obtained sufficiently and efficiently. As such a reducing agent (hydrogen source), from the viewpoint of reaction efficiency, formic acid is preferable.

Also, the above-mentioned base is not particularly limited, and known bases that can be used in the so-called reductive Heck reaction (for example, those exemplified in paragraph [0088] of International Publication No. 2015/163314, etc.) can be appropriately used. As such a base, from the viewpoint of improving the reaction yield, triethylamine, N,N-diisopropylethylamine, sodium acetate, potassium acetate are more preferable, and triethylamine, N, N-diisopropylethylamine, especially triethylamine. In addition, such a base may be used individually by 1 type, or may use it in combination of 2 or more types.

Furthermore, as the above-mentioned palladium catalyst, there is no particular limitation, and known palladium catalysts that can be used in the so-called reducing Heck reaction (for example, paragraph [0085] to paragraph [ 0087], etc.). As this palladium catalyst, in terms of reaction yield, it is more preferable to use palladium acetate, palladium chloride or the like to bond other ligands (other ion or other molecules: for example, in palladium acetate In the case of acetic acid, it is a complex formed by a complex ion or molecule other than acetate ion, especially a complex formed by using palladium acetate or p-palladium acetate to bond a ligand (other complex ions or other molecules). Compounds, preferably palladium acetate complexes bonded to ligands. And, as this kind can be used as the complex compound that palladium acetate is bonded ligand to form as this kind of palladium catalyst, can preferably utilize the complex compound that the palladium acetate bond phosphine ligand forms (can be obtained by Synthesizer of palladium acetate and phosphine compounds). Such a phosphine compound (a compound bonded to palladium acetate in the form of a phosphine ligand) is not particularly limited, and triphenylphosphine, tricyclohexylphosphine, dicyclohexylphenylphosphine, 1, 2-bis(diphenylphosphine)ethane, tri(o-tolyl)phosphine, etc., among which tri(o-tolyl)phosphine is more preferable.

Also, in the present invention, in the presence of the above-mentioned reducing agent, the above-mentioned base, and the above-mentioned palladium catalyst, the aromatic compound represented by the above-mentioned general formula (4) is combined with the alicyclic compound represented by the above-mentioned general formula (5) Compounds react. Such a reaction (reaction of the above-mentioned aromatic compound and the above-mentioned alicyclic compound) is preferably carried out in a solvent in which the above-mentioned reducing agent, the above-mentioned base, and the above-mentioned palladium catalyst are present. In this way, by using a solvent for the reaction, the reaction can be more efficiently performed in the solvent. As such a solvent, known solvents (for example, amide-based solvents, etc.) can be suitably used without particular limitation, and N,N-dimethylformamide is more preferably used in terms of further improvement in yield. Amines, N,N-Dimethylacetamide. Such a solvent may be used individually by 1 type, or may mix and use 2 or more types. In addition, the order of adding each component to a solvent etc. is not specifically limited. From the viewpoint of controlling the reaction, etc., it may be added appropriately. Here, the reaction between the above-mentioned aromatic compound and the above-mentioned alicyclic compound is an exothermic reaction, so there is a tendency that it is difficult to control the internal temperature. Therefore, for example, from the viewpoint of performing the reaction while controlling the internal temperature, it is also possible to prepare a solvent containing A solution of a reducing agent and an alkali, or a solution containing a reducing agent, an alkali, and an aromatic compound in a solvent, is added dropwise to a mixed solution containing a palladium catalyst, the above-mentioned alicyclic compound, and a solvent for reaction.

Moreover, in order to carry out such a reaction, in the present invention, it is preferable to use a mixed solution containing the above-mentioned solvent, the above-mentioned reducing agent, the above-mentioned base, the above-mentioned palladium catalyst, the above-mentioned aromatic compound, and the above-mentioned alicyclic compound. By using such a mixed liquid, since the mixed liquid contains the above-mentioned reducing agent, the above-mentioned base, and a palladium catalyst, the reaction can be advanced in the presence of these. Furthermore, the above mixed solution may further contain a compound bonded to palladium in the form of a ligand to form a complex in the mixed solution. Furthermore, when using such a mixed solution, the order of adding each component is not particularly limited. As a method of preparing the mixed solution, for example, when using a palladium catalyst containing a palladium complex, it can be suitably used. The following method, etc.: firstly, a solvent, a palladium catalyst (such as palladium acetate), and a compound bonded to palladium in the form of a ligand are mixed to obtain a mixture containing a palladium catalyst containing a palladium complex, and a solvent , adding a base, a reducing agent, the above-mentioned aromatic compound, and the above-mentioned alicyclic compound to the mixture, thereby obtaining the above-mentioned mixed liquid.

Also, the amount of the above-mentioned alicyclic compound used in this reaction is not particularly limited, but is preferably 0.5 to 10 moles, more preferably 1.5 to 5 moles, relative to 1 mole of the above-mentioned aromatic compound. . When the amount of the alicyclic compound used is more than the above-mentioned lower limit, the reaction efficiency tends to be improved compared with the case where it is less than the above-mentioned lower limit. On the other hand, when the usage-amount is below the above-mentioned upper limit, There is a tendency that the formation of by-products can be further suppressed compared with the case where the above-mentioned upper limit is exceeded.

Also, when the above-mentioned mixed liquid is used for advancing the reaction in a solvent as described above, the total amount of the above-mentioned aromatic compound and the above-mentioned alicyclic compound in the above-mentioned mixed liquid is preferably 1 to 80% by mass. , more preferably 5 to 50% by mass. When the total amount is above the above-mentioned lower limit, the reaction efficiency tends to increase compared with the case of less than the above-mentioned lower limit; Compared with the case, there is a tendency that the generation of by-products can be further suppressed.

Also, in the case of utilizing the above-mentioned mixed solution in order to carry out the reaction in a solvent as described above, the content of the palladium catalyst in the above-mentioned mixed solution is not particularly limited, and it is preferably set to be the molar amount of the palladium in the above-mentioned mixed solution. The molar amount is an amount of 0.00001 to 0.2 times the molar amount (more preferably 0.00005 to 0.05 times the molar amount) of the above-mentioned alicyclic compound. When the content of the palladium catalyst is more than the above-mentioned lower limit, the reaction efficiency tends to increase compared with the case where the above-mentioned lower limit is not reached; Compared with the case of the upper limit, there is a tendency that the excessive progress of the reaction can be suppressed, and the reaction can be more easily controlled.

Moreover, as content of the alkali in such a liquid mixture, it is preferable to set it as the quantity which is 1.0-5.0 times mole (more preferably about 2 times) with respect to the mole quantity of the said alicyclic compound. When the content of such a base is more than the above-mentioned lower limit, the reaction efficiency tends to increase compared with the case where the above-mentioned lower limit is not reached; Compared with the case, there is a tendency that the generation of by-products can be further suppressed.

Also, as the content of the above-mentioned reducing agent in the above-mentioned mixed solution, there is no particular limitation, and it is preferable to set the molar amount of the above-mentioned reducing agent as 1.0 to 5.0 times the molar amount of the above-mentioned alicyclic compound (more Preferably about 2 times the amount). If the content of such a reducing agent is less than the above-mentioned lower limit, the reaction rate tends to decrease. On the other hand, if it exceeds the above-mentioned upper limit, by-products tend to increase.

Also, there is no particular limitation on the reaction apparatus used for this reaction, and a container capable of introducing the above-mentioned reducing agent, the above-mentioned base, the above-mentioned palladium catalyst, the above-mentioned aromatic compound, and the above-mentioned alicyclic compound (such as , glass flasks or glass-lined kettles, etc.).

In addition, as the condition of the atmosphere gas when the above-mentioned reaction is carried out, an inert gas atmosphere is preferable from the viewpoint of the stability of raw materials and products. It does not specifically limit as such an inert gas, For example, nitrogen, helium, argon etc. are mentioned. For example, the reaction can be carried out by substituting the atmosphere gas in the container with nitrogen.

Also, the reaction temperature during this reaction is also different according to the type of raw material compound or palladium catalyst used, and is not particularly limited. In terms of obtaining higher reaction efficiency, etc., it is more preferably set at 65 to 50°C. 85°C, more preferably 70 to 80°C. In addition, the reaction time of such a reaction is preferably 0.5 to 20 hours (more preferably 2 to 15 hours). By making the conditions of such reaction temperature and reaction time into the said range, the carbonyl compound represented by said general formula (2) can be obtained more efficiently. Furthermore, the above-mentioned carbonyl compound obtained by this reaction becomes an ester compound in which ^R6 and ^R7 are groups other than hydrogen atoms in formula (2), but after obtaining the ester compound in this way, the The conversion of the ester group of R ⁶ and R ⁷ into a carboxylic acid group is carried out by a known method (for example, the method of heating in a lower carboxylic acid), thereby obtaining the above-mentioned formula in which R ⁶ and R ⁷ are hydrogen atoms. A carbonyl compound represented by the general formula (2).

By reacting the above-mentioned aromatic compound and the above-mentioned alicyclic compound in this way, the carbonyl compound represented by the above-mentioned general formula (2) can be obtained.

＜Polyimide＞ The polyimide of the present invention contains a polycondensate of a monomer (A) and a monomer (B) as a diamine compound. At least one compound of the group consisting of anhydrides and their derivatives.

Furthermore, it is generally known that polyimides form their polyadducts (addition polymers, Ring-opening polyadduct) is polyamic acid, which is obtained by ring-closing condensation (dehydration ring-closing: intramolecular condensation) of the obtained polyamic acid. In this way, since polyimide is generally a polymer obtained by the above-mentioned reaction, it can be said to be polycondensed by the above-mentioned monomer (A) and monomer (B) (the above-mentioned complex addition and the above-mentioned ring-closing condensation) The polycondensate obtained is polyimide. Hereinafter, first, the monomer (A) and the monomer (B) used to form such a polycondensate will be separately described.

〈Monomer (A)〉 The monomer (A) of this invention contains at least 1 sort(s) of compound chosen from the group which consists of tetracarboxylic dianhydride represented by the said General formula (1), and its derivative(s).

Here, the tetracarboxylic dianhydride represented by the said general formula (1) is the same as what was demonstrated as the tetracarboxylic dianhydride of this invention mentioned above (preferably also the same). Moreover, the tetracarboxylic dianhydride represented by such general formula (1) can be manufactured by the manufacturing method of the tetracarboxylic dianhydride of this invention mentioned above, and the manufacturing method of the carbonyl compound of this invention mentioned above.

Also, the derivatives of the tetracarboxylic dianhydride represented by the above-mentioned general formula (1) are not particularly limited, and are more preferably di Ester dicarboxylic acid, and diester dicarboxylic acid dichloride. That is, when using derivatives of the tetracarboxylic dianhydride represented by the above general formula (1), it is preferable to modify the tetracarboxylic dianhydride represented by the above general formula (1) into the corresponding diester Dicarboxylic acid, or diester dicarboxylic acid dichloride is used later. A method for producing such a derivative is not particularly limited, and known methods can be appropriately used. In the case of preparing a diester dicarboxylic acid dichloride suitable as a derivative of tetracarboxylic dianhydride represented by the above general formula (1), for example, the following method can be used: make the compound represented by the above general formula (1) The tetracarboxylic dianhydride reacts with any alcohol to obtain the diester dicarboxylic acid, and then reacts it with a chlorination reagent (thionyl chloride, oxalyl chloride, etc.) to obtain the corresponding diester dicarboxylic acid acid dichloride.

In addition, the monomer (A) of the present invention only needs to contain at least one compound selected from the group consisting of tetracarboxylic dianhydride represented by the above general formula (1) and its derivatives, and may further contain other Compound (another known monomer compound capable of producing polyimide by reacting with the monomer (B)). In this way, when the monomer (A) further includes other compounds, the monomer (A) is preferably selected from the group consisting of tetracarboxylic dianhydride represented by the above general formula (1) and its derivatives. At least one compound among them also includes "other tetracarboxylic dianhydrides" other than tetracarboxylic dianhydrides represented by the general formula (1) and/or derivatives thereof. In this way, the monomer (A) can be used as a compound containing at least one compound selected from the group consisting of tetracarboxylic dianhydrides represented by the above general formula (1) and derivatives thereof, and other tetracarboxylic dianhydrides. Anhydrides and/or derivatives thereof containing tetracarboxylic dianhydride-based monomers.

Such other tetracarboxylic dianhydrides are not particularly limited, and known ones that can be used for the production of polyimides can be appropriately used, for example, pyromellitic anhydride, 3,4'-oxydiphthalic anhydride, etc. Dicarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, biphenyl-3,4,3',4'-tetracarboxylic dianhydride, benzophenone-3,4,3', 4'-tetracarboxylic dianhydride, diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene) di-phthalate Dicarboxylic dianhydride, m-triphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, cyclobutane- 1,2,3,4-tetracarboxylic dianhydride, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride, cyclohexane-1,2 ,4,5-tetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, bis(1,3- Dioxo-1,3-dihydroisobenzofuran-5-carboxylate) 1,4-phenylene ester, nor-ale-2-spiro-α-cyclopentanone-α'-spiro-2"- Noralkane-5,5",6,6"-tetracarboxylic dianhydride (CpODA), compounds represented by the following formulas (6) to (7) (compounds represented by the following formula (6) (referred to as "BNBDA"), a compound represented by the following formula (7) (abbreviated as "BzDA")), etc.

[chemical 6]

Such other tetracarboxylic dianhydrides may be used individually by 1 type, or may use 2 or more types together. Furthermore, when utilizing such other tetracarboxylic dianhydrides, it is preferred that the content of other tetracarboxylic dianhydrides be 5 to 30 moles relative to the total molar amount of the compounds in the monomer (A). ear% way to use.

In addition, the monomer (A) of the present invention preferably contains tetracarboxylic dianhydride represented by the above general formula (1) and/or its derivatives as a main component. The total amount of dianhydride (the total amount of the compound), the content (total amount) of tetracarboxylic dianhydride represented by the above-mentioned general formula (1) and derivatives thereof (total amount) is preferably 70 mole % (more preferably 80 mole %, and more preferably 90 mol%, especially preferably 95 mol%) or more. In addition, since a monomer (A) can manufacture polyimide easily through manufacture of a polyamic acid, it can be used as what contains the tetracarboxylic dianhydride represented by the said general formula (1).

<Monomer (B): Diamine compound> The monomer (B) is a diamine compound. The diamine compound as such a monomer (B) is not particularly limited, and known compounds that can be used for producing polyimides can be appropriately used, and aromatic diamines and/or aliphatic diamines can be preferably used.

Such aromatic diamines are not particularly limited, and known ones that can be used in the manufacture of polyimides (for example, the aromatic diamines described in paragraph [0039] of Japanese Patent Application Laid-Open No. 2018-44180 can be appropriately used. amines, etc.). Moreover, it does not specifically limit as said aliphatic diamine, The well-known thing which can be used for polyimide manufacture can be used suitably. In addition, the above-mentioned aliphatic diamine may be an alicyclic one. Furthermore, such diamine compounds (preferably aromatic diamines and/or aliphatic diamines) may be compounds containing ester or amide bonds in their molecules, and furthermore, may be derivatives derived from diamines. Thus, in the present invention, the term "diamine compound" is a concept including not only diamine itself but also derivatives thereof. In addition, as such a derivative, an alkylamine and an alkylsilylamine are mentioned, for example.

As such diamine compounds, for example, 1,4-diaminotoluene, 1,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 4, 4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenyl ether 3,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl ether, 2,4'- Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenylene, 3,3'-diaminodiphenylene, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzamide, 3,3' -Diaminobenzophenone, bis(4-aminophenyl)sulfide, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) ) butane, 1,5-bis(4-aminophenoxy)pentane, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,2-bis [2-(4-Aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl) fluorene, 5(6)-amino-1-(4-aminomethyl base)-1,3,3-trimethylindan, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3 -Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4 '-Bis(3-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy) Phenyl]pyridine, bis[4-(4-aminophenoxy)phenyl]pyridine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3,3 '-Dicarboxy-4,4'-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl , 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3',4,4'-tetraaminobiphenyl, 1,3-bis(3-aminopropyl ) Tetramethyldisiloxane 1,6-diaminohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-methylene Bis(4-cyclohexylamine), trans-1,4-cyclohexanediamine, bicyclo[2.2.1]heptanebis(methylamine), tricyclo[3.3.1.13,7]decane-1 ,3-diamine, 4-aminophenyl 4-aminobenzoate, 2-(4-aminophenyl)aminobenzoxazole, 9,9-bis[4-(4-aminophenyl Oxy)phenyl]Terrene, 2,2'-bis(3-sulfopropoxy)-4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy) Biphenyl-3,3'-disulfonic acid, etc. In addition, such a diamine compound may be used individually by 1 type, or may use it in combination of 2 or more types.

Also, as such diamine compounds, 2,2'-bis(trifluoromethyl)benzidine (alias "2,2'-bis(trifluoromethyl)-[1,1'- Biphenyl]-4,4'-diamine", abbreviated as: TFMB), 4,4'-diaminodiphenyl ether (abbreviated as: 4,4'-DDE), 4,4'-diaminobenzyl Acylaniline (abbreviation: DABAN), 2,2'-dimethyl-[1,1'-biphenyl]-4,4'-diamine (abbreviation: MTD), p-phenylenediamine (alias "p-diamine Benzene", referred to as: PPD), bis(4-aminophenyl) terephthalate (abbreviated: BPTP), 4,4'-((propane-2,2-diylbis(4,1 -phenylene))bis(oxyl))diphenylamine (abbreviation: BAPP), 4,4'-(1,3-phenylene bis(oxyl))diphenylamine (abbreviation: TPE-R), 4 ,4'-([1,1'-biphenyl]-4,4'-diylbis(oxyl))diphenylamine (abbreviation: BODA), 4,4'-(9H-Oxyl-9,9- Diyl) diphenylamine (abbreviation: FDA), more preferably TFMB, 4,4'-DDE, DABAN, MTD, PPD, BPTP, BAPP, TPE-R, BODA, FDA, and more preferably TFMB, DABAN, PPD , FDA. In addition, the method for producing such a diamine compound is not specifically limited, A well-known method can be suitably used. Moreover, such a diamine compound can also utilize what is marketed suitably.

<Characteristics of polyimide, etc.> The polyimide of the present invention contains a polycondensate of a monomer (A) and a monomer (B) as a diamine compound. At least one compound of the group consisting of anhydrides and their derivatives.

The polycondensate of such polyimide monomer (A) and monomer (B) contains at least tetracarboxylic dianhydride and/or its derivatives and diamine compound represented by the above formula (1). The repeat unit formed by the reaction. Therefore, the polyimide, for example, can be made to have a repeating unit (I) represented by the following formula (10) and a repeating unit (II) represented by the following formula (11). At least 1 repeating unit.

[chemical 7]

[In the formula (10), Ar represents the residue obtained by removing two amino groups from the above-mentioned diamine compound (preferably an arylylene group with 6 to 50 carbon atoms, more preferably an arylylene group with 6 to 40 carbon atoms , and more preferably an aryl group with 6 to 30 carbons, especially an aryl group with 12 to 20 carbons), R ¹ to R ⁵ are respectively synonymous with R ¹ to R ⁵ in the above general formula (1) (preferably also synonymous)]

[chemical 8]

[In formula (11), Ar ¹ and Ar ² independently represent residues obtained by removing two amine groups from the above-mentioned diamine compound (preferably an aryl group with 6 to 50 carbons, more preferably a carbon number 6 to 40 aryl groups, preferably 6 to 30 carbons, especially preferably 12 to 20 carbons), R ¹ to R ⁵ are respectively the same as in the above general formula (1) R ¹ to R ⁵ are synonymous (preferably also synonymous)].

Also, when the polyimide of the present invention has the above-mentioned repeating units (I) and/or (II), the content (total amount) of the above-mentioned repeating units (I) and (II) is not particularly limited. The content (total amount) of (I) and (II) of all the repeating units in the polyimide is preferably 70-100 mol%, more preferably 90-100 mol%, especially preferably 100 mol% . By making the content (total amount) of the above-mentioned repeating units (I) and (II) more than the above-mentioned lower limit, compared with the case where it is set to be less than the above-mentioned lower limit, it is possible to increase the stability when it is made into a polyimide film. Film forming property and toughness can improve transparency and heat resistance, and can reduce CTE. Furthermore, when the above-mentioned monomer (A) contains tetracarboxylic dianhydride and/or its derivatives represented by the above-mentioned general formula (1) and other tetracarboxylic dianhydrides and/or its derivatives, Furthermore, the polyimide of this invention has the structure (other repeating unit) obtained by polycondensing other tetracarboxylic dianhydride and/or its derivative(s), and a diamine compound (component (B)).

In addition, the polyimide of the present invention preferably has a glass transition temperature (Tg) of 300° C. or higher, and more preferably has a glass transition temperature (Tg) of 350° C. ℃ above. In addition, such a glass transition temperature (Tg) can be measured in tension mode using the thermomechanical analysis apparatus (Rigaku product name "TMA8310").

Furthermore, the polyimide of the present invention is preferably a 5% weight loss temperature of 450° C. or higher, more preferably a 5% weight loss temperature of 470° C. ℃ above. Furthermore, such a 5% weight loss temperature can be obtained by raising the temperature from room temperature (for example, 25° C.) to 40° C. under a nitrogen atmosphere while blowing nitrogen gas, and then setting 40° C. as the measurement start temperature. Heating is carried out gradually, and the temperature at which the weight of the sample used is lost by 5% is measured.

In addition, as the polyimide of the present invention, it is preferably a 1% weight loss temperature of 400° C. or higher, more preferably a 1% weight loss temperature of 420° C. ℃ above. Furthermore, such a 1% weight loss temperature can be obtained by raising the temperature from room temperature (for example, 25° C.) to 40° C. under a nitrogen atmosphere while blowing nitrogen gas, and then setting 40° C. as the measurement start temperature. Heating is carried out gradually, and the temperature at which the weight of the sample used is lost by 1% is measured.

In addition, as the polyimide of the present invention, when forming a film, it is more preferable that the yellowness (YI) is 20 or less ( Furthermore, it is preferably 10 or less). Such yellowness (YI) can be obtained by measuring according to ASTM E313-05 (published in 2005).

As the polyimide of the present invention, when forming a film, it is more preferable that the haze (HAZE: haze) is 15 or less from the viewpoint that it can be efficiently used according to applications such as transparency. (More preferably 5 or less). In addition, haze (turbidity) can be calculated|required by measuring based on JISK7136 (issued in 2000).

In addition, the number average molecular weight (Mn) of such polyimide is preferably 1,000 to 1,000,000 in terms of polystyrene. The weight average molecular weight (Mw) of such polyimide is preferably 1,000 to 5,000,000 in terms of polystyrene. Furthermore, the molecular weight distribution (Mw/Mn) of such polyimide is preferably 1.1-5.0. When the molecular weight (Mw or Mn) or molecular weight distribution (Mw/Mn) of such polyimide is within the above range, a more uniform film can be produced more efficiently. Furthermore, the molecular weight (Mw or Mn) or molecular weight distribution (Mw/Mn) of such polyimide can be measured using a gel permeation chromatography (GPC) measuring device (manufactured by Tosoh Co., Ltd., commercial product Name: HLC-8320GPC/4 columns: Tosoh Co., Ltd., trade name: TSK gel Super AW4000, 3000, 2500, Super H-RC, solvent: N,N-dimethylacetamide (DMAc) ) for measurement, and obtained by converting the measured data into polystyrene. Furthermore, when it is difficult to measure the molecular weight of such polyimides, the molecular weight can be inferred based on the viscosity of the polyamic acid used to manufacture the polyimides, and the corresponding polyimides can be screened out according to the application. Amides are used.

Also, the polyimide of the present invention can also be made to have solubility in solvents, therefore, it can also be dissolved in an organic solvent and used in the form of a polyimide solution (resin solution: varnish), and then Or, as the organic solvent used in this polyimide solution, from the viewpoints of solubility, film-forming property, productivity, industrial availability, availability of existing equipment, price, etc., N-methyl -2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, propylene carbonate, tetramethylurea, 1,3-di Methyl-2-imidazolidinone, cyclopentanone, more preferably N-methyl-2-pyrrolidone, N,N-dimethylacetamide, γ-butyrolactone, tetramethylurea, especially Preferred are N,N-dimethylacetamide and γ-butyrolactone. In addition, such an organic solvent may be used individually by 1 type, or may use it in combination of 2 or more types.

In addition, when the polyimide of the present invention is used as a polyimide solution, it can also be preferably used as a coating liquid or the like for producing various processed products. For example, when forming a film, a polyimide film can be formed by applying a polyimide solution on a substrate to obtain a coating film, and then removing the solvent. Furthermore, in such a polyimide solution, the content (dissolved amount) of the above-mentioned polyimide is not particularly limited, but is preferably 1-75% by mass, more preferably 10-50% by mass.

In addition, the polyimide of the present invention can be used by appropriately containing known components according to its use, for example, it may further contain other polymers, antioxidants, ultraviolet absorbers-hindered amine light stabilizers, nucleating agents-translucent agents , Inorganic fillers (glass fibers, glass hollow balls, talc, mica, alumina, titanium oxide, silicon dioxide, etc.), heavy metal deactivators-additives for filler-filled plastics, flame retardants, processability improvers-lubricant/ Water-dispersed stabilizers, permanent antistatic agents, toughness enhancers, surfactants, carbon fibers and other additives are used.

Moreover, the shape of the polyimide is not particularly limited, for example, it can be made into a film or powder, or it can be further made into a pellet shape by extrusion. In this way, the polyimide of the present invention can be formed into a film, or can be formed into pellets by extrusion molding, or can be appropriately formed into various shapes by known methods.

＜Polyimide Precursor Resin＞ The polyimide precursor resin of the present invention contains a polyadduct of a monomer (A) and a monomer (B) as a diamine compound. At least one compound in the group consisting of tetracarboxylic dianhydride and its derivatives.

Here, the polyimide precursor resin of this invention should just be what double-added the said monomer (A) and the said monomer (B). That is, the polyimide precursor resin system of the present invention includes the concept of derivatives obtained from the addition polymer in addition to the polyadduct of the above-mentioned monomer (A) and the above-mentioned monomer (B) ( For example, in addition to polyamic acid, which is an addition polymer (ring-opening polyadduct) obtained by double addition of tetracarboxylic dianhydride represented by the above general formula (1) and a diamine compound, is a derivative obtained from the addition polymer). In addition, such a polyimide precursor resin only needs to contain a structure (repeating unit) obtained by complex addition of tetracarboxylic dianhydride represented by the above general formula (1) and/or its derivatives with a diamine compound. It only needs to be a derivative thereof, and may further have a structure (other repeating unit) obtained by complex addition of other tetracarboxylic dianhydride and/or derivatives thereof and a diamine compound. Furthermore, in the polyimide precursor resin of the present invention, both "monomer (A)" and "monomer (B)" have the same meaning as those described above for the polyimide of the present invention.

Moreover, as a repeating unit which the polyimide precursor resin of this invention may contain, the repeating unit (III) represented by following General formula (12), for example can be illustrated.

[chemical 9]

[In formula (12), Ar represents the residue obtained by removing two amine groups from the above-mentioned diamine compound (preferably an arylylene group with 6 to 50 carbon atoms, more preferably an arylylene group with 6 to 40 carbon atoms , and more preferably an aryl group with 6 to 30 carbons, especially an aryl group with 12 to 20 carbons), R ¹ to R ⁵ are respectively synonymous with R ¹ to R ⁵ in the above general formula (1) (The preferred ones are also synonymous), ^Y1 each independently represent one species selected from the group consisting of a hydrogen atom, an alkyl group with a carbon number of 1 to 6, and an alkylsilyl group with a carbon number of 3 to 9, represented by a One of the bonding bond and the bonding bond represented by b is bonded to the carbon atom represented by *1, and the other of the bonding bond represented by a and the bonding bond represented by b is bonded to *2 The carbon atom represented by c is bonded, one of the bond represented by c and the bond represented by d is bonded to the carbon atom represented by *3, and the bond represented by c and the bond represented by d The other one of the bonding bonds is bonded to the carbon atom represented by *4] Furthermore, as the polyimide precursor resin of the present invention, one containing the above-mentioned repeating unit (III) is more preferable.

In this repeating unit (III), ^Y in the formula independently represent an alkyl group selected from a hydrogen atom, an alkyl group with 1 to 6 carbons (preferably 1 to 3 carbons) and an alkane with 3 to 9 carbons. One of the group consisting of silyl groups. Such ^Y1 can be changed by appropriately changing the type of the substituent, the introduction rate of the substituent, and appropriately changing the production conditions. Furthermore, in the case where Y ¹ is all hydrogen atoms (when it becomes a repeating unit of so-called polyamic acid), polyimide can be efficiently produced by dehydrating and closing the ring. Also, when Y in the above-mentioned general formula (12) is an alkyl group having ¹ to 6 carbons (preferably 1 to 3 carbons), the storage stability of the polyimide precursor resin becomes lower. better trend. The alkyl group having 1 to 6 carbon atoms that can be used as Y ¹ is more preferably a methyl group or an ethyl group. Moreover, when ^Y1 in the said general formula (12) is an alkylsilyl group with 3-9 carbon atoms, there exists a tendency for the solubility of a polyimide precursor resin to become more excellent. The alkylsilyl group having 3 to 9 carbon atoms that can be selected as Y ¹ is more preferably a trimethylsilyl group or a tertiary butyldimethylsilyl group.

Regarding Y ¹ in the above-mentioned repeating unit (III), the introduction rate of groups other than hydrogen atoms (alkyl and/or alkylsilyl groups) is not particularly limited, and all the groups contained in the polyimide precursor resin In the case where at least a part of all ^Y1 in the repeating unit (III) is an alkyl group and/or an alkylsilyl group, it is preferably 25% or more of the total amount of ^Y1 in the above repeating unit (III) (More preferably 50% or more, and more preferably 75% or more) as an alkyl group and/or an alkylsilyl group (moreover, in this case, ^Y1 other than an alkyl group and/or an alkylsilyl group is A hydrogen atom). By making 25% or more of the total amount of ^Y1 into an alkyl group and/or an alkylsilyl group, there exists a tendency for the storage stability of a polyimide precursor resin to become more excellent.

Also, in the above general formula (12), the bond represented by a and the bond represented by b are bonded to the carbon atom *1 (the carbon atom marked with *1) forming the noralkane ring. One of them, and the other one of the bond represented by a and the bond represented by b is bonded to the carbon atom *2 (the carbon atom marked with *2) forming the norphane ring By. Also, in the above-mentioned general formula (12), one of the bonding bond represented by c and the bonding bond represented by d is bonded to the carbon atom *3 (the carbon atom marked with symbol *3) forming the benzene ring. One, and the other one of the bond represented by c and the bond represented by d is bonded to the carbon atom *4 (the carbon atom marked with *4) forming the norphane ring.

Also, when the polyimide precursor of the present invention has the above-mentioned repeating unit (III), the content of the above-mentioned repeating unit (III) is not particularly limited, relative to all the repeating units in the polyimide precursor, Preferably it is 70-100 mol%, more preferably 90-100 mol%, especially preferably 100 mol%. By making content of the said repeating unit (II) more than the said minimum, the yellowness of a polyimide can be further reduced at the time of polyimide manufacture compared with the case where it is less than the said minimum.

Moreover, the intrinsic viscosity [η] of the polyimide precursor (preferably polyamic acid) is preferably 0.05-3.0 dL/g, more preferably 0.1-2.0 dL/g. By making such intrinsic viscosity [η] more than the above-mentioned lower limit, compared with the case where it is set to be less than the above-mentioned lower limit, when using it to produce a polyimide film, the strength of the obtained film can be improved. On the other hand, by setting it below the above-mentioned upper limit, compared with the case of exceeding the above-mentioned upper limit, processability becomes excellent from the viewpoint of viscosity, for example, when it is used to produce a film, wrinkles can also be suppressed. The production can efficiently produce a uniform film. Also, in this specification, regarding the "intrinsic viscosity [η]" of the polyimide precursor (preferably polyamic acid), for example, use a dilute solvent (for example, N,N-dimethylacetamide ( DMAc)) to prepare a test sample (solution) with a polyimide precursor concentration of 0.5 g/dL, use the test sample, and use a dynamic viscometer to measure the viscosity of the above test sample at a temperature of 30°C , take the obtained value as the intrinsic viscosity [η]. In addition, as such a dynamic viscometer, the automatic viscosity measuring apparatus (trade name "miniPV (registered trademark)-HX") manufactured by CANNON INSTRUMENT COMPANY was used.

Again, this polyimide precursor (preferably polyamic acid) can be preferably utilized when making the polyimide of the present invention (can be used as a reaction intermediate when making the polyimide of the present invention (precursor) form).

Furthermore, the polyimide precursor resin (preferably polyamic acid) of the present invention can be contained in an organic solvent and used in the form of a polyimide precursor resin solution (varnish). The organic solvent used in the polyimide precursor resin solution (varnish) is not particularly limited, and known ones can be appropriately used, for example, paragraph [0175] of International Publication No. 2018/066522 can be appropriately used and the solvents described in paragraphs [0133] to [0134]. Moreover, the content of the polyimide precursor resin in the polyimide precursor resin solution is not particularly limited, but is preferably 1-80% by mass, more preferably 5-50% by mass. In addition, well-known additives, such as an antioxidant, an ultraviolet absorber, and a filler, can be suitably added to such a polyimide precursor resin solution according to the purpose of use, etc.

<About the method for producing polyimide precursor and polyimide> A method that can be preferably used as a method for producing the polyimide precursor of the above-mentioned present invention and the polyimide of the above-mentioned present invention will be briefly described. First, a method that can be preferably used as a method for producing the above-mentioned polyimide precursor of the present invention will be described.

The method that can be preferably used as a method for manufacturing the above-mentioned polyimide precursor of the present invention is not particularly limited, for example, the following method can be exemplified: in the presence of an organic solvent, make the compound selected from the above general formula (1) The monomer (A) of at least one compound in the group consisting of tetracarboxylic dianhydride and its derivatives represented by (1) is obtained by addition polymerization reaction with the above-mentioned monomer (B) which is a diamine compound. Polyimide precursor.

As the organic solvent used in this method, preferably an organic solvent capable of dissolving both the above-mentioned monomer (A) and the above-mentioned monomer (B) (and preferably also capable of making the formed polyimide precursor soluble organic solvents). Such an organic solvent is not particularly limited, and those that can be used for the production of polyimides can be appropriately used, for example, N-methyl-2-pyrrolidone (NMP), N,N-dimethyl Acetamide (DMAc), N,N-dimethylformamide, γ-caprolactone (GBL), tetramethylurea (N,N,N',N'-tetramethylurea: TMU), di Methyl sulfide, δ-valerolactone, etc. Such organic solvents may be used alone or in combination of two or more.

As the amount of the above-mentioned organic solvent used, it is preferable that the total amount of the monomers used in the reaction (the total amount of the above-mentioned monomer (A) and the above-mentioned monomer (B)) is 5 to 40% by mass relative to the total amount of the reaction solution. % (more preferably 10-25% by mass). When the usage-amount of such an organic solvent exists in the said range, polyamic acid can be obtained efficiently.

In addition, when the total amount of the compound in the above-mentioned monomer (A) used in the reaction is converted into 1 mole, the usage-amount of the diamine compound as the above-mentioned monomer (B) is preferably set to The number of moles of the diamine compound is 0.9 to 1.1 moles, and it is preferable to set the number of moles of the diamine compounds to be 0.95 to 1.05 moles from the viewpoint that the degree of polymerization can be further increased.

In addition, the reaction temperature when the above-mentioned monomer (A) and the above-mentioned monomer (B) are subjected to the addition polymerization reaction is not particularly limited as long as it is appropriately adjusted to a temperature at which the addition polymerization reaction can be performed, and is preferably To set it at 15 to 100°C. Also, when carrying out this kind of addition polymerization, for example, when the monomer (A) contains the tetracarboxylic dianhydride represented by the above-mentioned general formula (1), the following method can be used: under atmospheric pressure, or nitrogen, helium Under an atmosphere of inert gas such as gas, argon, etc., a solution containing the tetracarboxylic dianhydride (monomer (A)) represented by the above general formula (1) and the above diamine compound (monomer (B)) was placed in the above-mentioned The reaction is carried out while stirring at the reaction temperature for 10 to 100 hours, but the method is not particularly limited. In this way, the polyamide acid ( Including Y in formula (12) ¹ is the polyimide precursor of the repeating unit (II) of hydrogen atom).

Here, in the case of producing a polyimide precursor resin containing a repeating unit (II) in which Y in formula (12) is a hydrogen atom, as its production ^method , for example, the following method can be suitably adopted: Except using the tetracarboxylic dianhydride represented by the above general formula (1) as the tetracarboxylic dianhydride, in the same manner as the method described in paragraphs [0165] to [0174] of International Publication No. 2018/066522 to manufacture.

Next, a method that can be preferably used as a method for producing the above-mentioned polyimide of the present invention will be described. The method for producing the above-mentioned polyimide of the present invention is not particularly limited, for example, when using the compound represented by the above-mentioned general formula (1) as the monomer (A), in addition to using the above-mentioned general formula (1) In addition to the compound shown as tetracarboxylic dianhydride, a known method for producing polyimide by reacting tetracarboxylic dianhydride and diamine (for example, described in International Publication No. 2011/099518) can be suitably used. method, the method described in International Publication No. 2015/163314, the method described in Japanese Patent Application Laid-Open No. 2018-044180, the method described in International Publication No. 2018/066522, etc.). Furthermore, the method that can be preferably used as a method for producing the polyimide of the present invention is not particularly limited, for example, the following method can be exemplified: the polyimide precursor resin (preferably polyamic acid), and then imidize the polyimide precursor resin by ring-closing condensation (dehydration ring-closing: intramolecular condensation), thereby obtaining polyimide. Also, the method (conditions, etc.) for imidization by ring-closing condensation of the above-mentioned polyimide precursor resin (preferably polyamic acid) is not particularly limited, and known imides can be suitably used. The method (conditions) adopted in the imidization method (for example, the imidization method described in International Publication No. 2011/099518, etc.). [Example]

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.

(Synthesis Example 1: Synthesis of dimethyl 4-bromophthalate) After purging the inside of a 1 L flask with a reflux tube with nitrogen, first, 4-bromophthalic anhydride (80.0 g, 352 mmol) was added to the above flask, methanol (400 mL) was added, and then Hydrochloric acid (8.0 mL, concentration of HCl: 35% by mass) was added to obtain a mixed solution. Next, the above liquid mixture was heated and refluxed for 29 hours to obtain a reaction liquid. Furthermore, as a result of gas chromatography analysis (GC analysis) of the reaction liquid obtained by such heating and reflux, it was confirmed that the purity of dimethyl 4-bromophthalate was 86.8 area%. In addition, the conditions used for this GC analysis are as follows.

<GC measurement condition 1> Column: HP-5MS UI (manufactured by Agilent Technologies, Inc.) Column flow: 1.2 mL/min Injection volume: 1 μL Injection port: 200°C, 8.9 psi, split ratio 97.1:1 Heating conditions in the oven: keep at 100°C for 2 minutes, then raise the temperature to 300°C at a rate of 10°C/min, and keep at 300°C for 1 minute. Detector: FID (flame ionization detector, flame ionization detector), 300°C.

Next, after methanol was distilled off under reduced pressure from the obtained reaction liquid, ethyl acetate (400 mL) was added, and the ethyl acetate solution was obtained. Next, the ethyl acetate solution thus obtained was washed twice with saturated sodium bicarbonate water (160 mL), and then washed once with water (160 mL). Next, the solvent was distilled off from the washed ethyl acetate solution to obtain a residue. For the residue obtained in this way, vacuum drying was carried out at room temperature (about 25°C), thereby obtaining dimethyl 4-bromophthalate (77.7 g, 284 mmol, yield Yield: 80.1%, purity (confirmed by GC analysis): 100 area%, which is a compound corresponding to the compound represented by the above general formula (4)). In addition, the measurement conditions of this GC analysis were the same conditions as the above-mentioned <GC measurement conditions 1>.

(Example 1) Tris(o-tolyl)phosphine (579 mg, 1.90 mmol) and palladium acetate (Pd(OAc) ₂ , 214 mg, 0.951 mmol) were added to a 1 L flask purged with nitrogen , and further adding N,N-dimethylformamide (150 mL, abbreviation: DMF) to obtain a mixed solution. Thereafter, nitrogen gas was passed into the flask (under nitrogen flow), and the above mixed solution was stirred at 50° C. for 30 minutes, thereby forming tri(o-tolyl)phosphine as a ligand in the above mixed solution. palladium complex. Then, for the mixed solution (yellow solution) comprising the above-mentioned palladium complex, add 4-bromophthalic acid dimethyl ester (57.2 g, 209 mmol, which is equivalent to the above-mentioned general formula (4 ) represented by the compound (one of the raw material compounds)) and dimethyl-resistant acid dimethyl ester (40.0 g, 190 mmol, which is a compound (one of the raw material compounds) corresponding to the compound represented by the above general formula (5) )) to obtain the raw material mixture. Then, a solution containing triethylamine (38.5 g, 381 mmol), formic acid (17.5 g, 381 mmol) and DMF (96.0 mL) was added to the raw material mixture obtained in this way to obtain a reaction mixture . Thereafter, the temperature of the mixture used for the above reaction was raised to 80° C., and maintained at 80° C. for 5 hours, whereby dimethyl 4-bromophthalate and dimethyl-resistant acid were reacted in the above mixture , to obtain a reaction solution. Furthermore, GC analysis was performed on the reaction solution obtained in this way, and it was confirmed that two kinds of raw material compounds (dimethyl 4-bromophthalate and dimethyl-resistant acid) disappeared. The calculated yield of the reaction product in the mixture was 67.1%. In addition, the conditions used for this GC analysis are as follows.

<GC measurement condition 2> Column: HP-5MS UI (manufactured by Agilent Technologies, Inc.) Column flow: 1.2 mL/min Injection volume: 1 μL Injection port: 320°C, 9.5 psi, split ratio 97.1:1 Heating conditions in the oven: keep at 100°C for 2 minutes, then raise the temperature to 320°C at a rate of 10°C/min, and keep at 320°C for 16 minutes. Detector: FID, 340°C.

Next, water (246 mL) was added to the reaction solution obtained above, and extraction was performed twice with toluene (400 mL) to obtain a toluene solution. Next, hydrochloric acid (HCl concentration: 5% by mass, 205 mL), saturated sodium bicarbonate water (205 mL), and water (205 mL) were each used once in the order described, and the toluene solution was washed. Then, after the organic layer was separated from the solution after washing, the obtained organic layer was filtered, and then the solvent was distilled off under reduced pressure to obtain a crude product (83.1 g, calculated from Rate: 62.4%, content rate in toluene solution (calculated by GC analysis): 57.8% by mass) (procedure of obtaining crude product). Here, the calculated yield refers to the yield calculated from the added amount (used amount) of the raw material compound used for production relative to the theoretical amount of the product (hereinafter used in the same meaning). In addition, the measurement conditions of this GC analysis were the same conditions as the above-mentioned <GC measurement conditions 2>.

Next, carry out above-mentioned " the step of obtaining crude product " additionally with the same method as above, and prepare the crude product (HPLC (high performance liquid chromatography, high performance liquid chromatography) purity of 73.1 area that total amount is 182 g %). Then, 182 g of the obtained crude product was purified by silica gel flash column chromatography, thereby obtaining a product containing a pale yellow oily substance. That is, when performing such purification, first, after filling the column with silica gel in an amount 2.5 times the mass of the crude product, a solution obtained by dissolving the crude product in the mobile phase solvent is infiltrated into the obtained column. Furthermore, as the mobile phase solvent, a mixed solution of heptane and ethyl acetate is used, and as shown in Figure 1, depending on the number of determinations, the volume ratio of heptane and ethyl acetate in the mobile phase solvent (heptane/ Ethyl acetate) was gradually changed from 4/1 to 2/1, thereby gradually changing the polarity of the above-mentioned mobile phase solvent, while performing multiple measurements (a total of 30 measurements). Furthermore, as shown in Fig. 1, in the measurement from the 1st to the 10th time, the volume ratio of heptane to ethyl acetate is 4/1 solvent, and in the measurement from the 11th to the 24th time, A solvent with a volume ratio of heptane to ethyl acetate of 3/1 was used, and a solvent with a volume ratio of heptane to ethyl acetate of 2/1 was used for the 25th to 30th measurements. In addition, when performing such a measurement, after each measurement, the substance adsorbed on the column is eluted, and the eluate is collected separately. After performing multiple measurements in this way, by thin-layer chromatography (TLC), confirm the number of measurements (16th to 25th) that the substance is adsorbed at the position that coincides with the spot of the target object. The eluate (dissolved fraction) of the number of measurements (16th to 25th) was combined, and then the solvent was distilled off from the obtained eluate to obtain 107 g of a product containing a light yellow oily substance (Recovery rate with respect to crude product: 58.8 mass %). Furthermore, when carrying out the above TLC, a solvent with a volume ratio of heptane to ethyl acetate of 1/1 was used, ultraviolet light (UV) was used for detection, and an aqueous solution containing KMn ₂ O ₇ and K ₂ CO ₃ was used as a TLC monitor. color reagents.

In order to confirm the structure of the product obtained in this way, NMR ( ¹ H-NMR, ¹³ C-NMR) measurement was performed. In the NMR measurement, an NMR measuring machine (manufactured by Varian, 600 MHz NMR) was used, and CDCl ₃ was used as a solvent. The ¹ H-NMR (CDCl ₃ ) and ¹³ C-NMR (CDCl ₃ ) spectra of the product obtained in this way are shown in Figs. 2 and 3, respectively. From the results shown in Figure 2 and Figure 3, it was confirmed that the obtained product was a carbonyl compound represented by the following formula (A) (compound name: 5-(3,4-bis(methoxycarbonyl)phenyl) Bicyclo[2.2.1]heptane-2,3-dicarboxylate (dimethyl 5-(3,4-bis(methoxycarbonyl)phenyl)bicyclo[2.2.1]heptane-2,3-dicarboxylate), referred to as :PNBTE).

[chemical 10]

From these results, it was found that in Example 1, 107 g (265 mmol) of PNBTE was obtained.

In addition, the purity of this product (PNBTE) was measured by HPLC, and it was confirmed that the purity was 99.9 area%. In addition, as conditions of the HPLC measurement for measuring the purity of a crude product and a product, the conditions described below were used.

<HPLC measurement conditions> Column: ZORBAX SB-C18 (2.1×150 mm, 1.8 μm) (manufactured by Agilent Technologies, Inc.) Mobile phase: Acetonitrile (MeCN)/water (H ₂ O) = 7/3 (volume ratio ) Flow rate: 0.150 mL/min Detector: DAD (diode array detector, diode array detector), 254 nm Temperature: 35°C.

(Example 2) The PNBTE (53.5 g, 132 mmol) obtained in Example 1 was dissolved in ethyl acetate to prepare an ethyl acetate solution (125 mL). Next, the above ethyl acetate solution and acetic acid (450 g) were added to a 1 L flask with a reflux tube. Then, after replacing the atmosphere in the flask with nitrogen, nitrogen was passed into the flask (under a nitrogen stream), and the mixture of the ethyl acetate solution and the acetic acid was heated at 125° C. for 2.5 hours, thereby automatically The above mixture extracted ethyl acetate along with acetic acid. Furthermore, this heating was carried out while replenishing the same amount of acetic acid as the extracted acetic acid in such a manner that the liquid volume in the flask was substantially constant. After such heating, a solution of trifluoromethanesulfonic acid (993 mg, 6.61 mmol, abbreviation: TfOH) dissolved in acetic acid (30.5 g) was added to the above-mentioned flask, and a mixed solution (containing PNBTE , a mixture of acetic acid and TfOH). Thereafter, the above mixture was heated for 7.5 hours under nitrogen flow (heating condition: the flask was heated in an oil bath at 135° C.). Furthermore, the heating of this mixed solution is carried out in a manner of extracting a part of vapor (acetic acid, etc.) while refluxing (under reflux conditions). In addition, when heating the mixed liquid, the step of adding new acetic acid dropwise into the flask was performed simultaneously so that the liquid volume of the mixed liquid would not decrease rapidly. Then, the heating of such a mixed solution and the dripping of acetic acid were calculated so that the density|concentration of the reaction product (acid dianhydride) in a mixed solution might become 40 mass % after 7.5 hours (after completion|finish of heating). By heating this mixture, a solution of the reaction product in a concentrated state is obtained. Furthermore, the calculation of the concentration (40% by mass) of the reaction product (acid dianhydride) in the mixed solution after this heating is based on the assumption that all of the PNBTE is reacted, and the obtained compounds (reaction products) all become the following formula ( B) Tetracarboxylic dianhydride represented by (compound name: 5-(1,3-dioxo-1,3-dihydroisobenzofuran-5-yl) hexahydro-4,7-methylene Isobenzofuran-1,3-dione (5-(1,3-dioxo-1,3-dihydroisobenzofuran-5-yl)hexahydro-4,7-methanoisobenzofuran-1,3-dione), abbreviation: PNBDA) (Assume that the conversion rate is 100%).

[chemical 11]

Then, the solution (concentrate) of the heated reaction product (acid dianhydride) was allowed to cool slowly overnight (about 15 hours), whereby the solid component (white powder) was precipitated in the solution (at 85 ℃ around the beginning of precipitation). Thereafter, the solid content was filtered off at room temperature, and then washed with ethyl acetate (32.1 mL) cooled to about 4°C. Then, the washed solid content was vacuum-dried at 80° C. to obtain 19.2 g of a white granular solid product.

In order to confirm the structure of the product obtained in this way, NMR ( ¹ H-NMR, ¹³ C-NMR) measurement was performed. In the NMR measurement, an NMR measuring machine (manufactured by Varian, 600 MHz NMR) was used, and dimethylsulfoxide-D6 (DMSO-D6) was used as a solvent. ¹ H-NMR (DMSO-D6) and ¹³ C-NMR (DMSO-D6) spectra of the product obtained in this way are shown in Fig. 4 and Fig. 5, respectively. From the results shown in FIGS. 4 and 5 , it was confirmed that the obtained product was tetracarboxylic dianhydride (PNBDA) represented by the above formula (B). From these results, it can be seen that in Example 2, 19.2 g (61.5 mmol, calculated yield: 46.5%) of PNBDA was obtained. In addition, the purity of the obtained product (PNBDA) was determined by HPLC measurement, and the purity was confirmed to be 98.8 area%. In addition, as the conditions of the HPLC measurement, the same conditions as <HPLC measurement conditions> described in Example 1 were used (the same conditions as the HPLC measurement conditions used for measuring the purity of PNBTE were used).

(Example 3) Tris(o-tolyl)phosphine (9.85 g, 32.3 mmol) and palladium acetate (Pd(OAc) ₂ , 3.63 g, 16.2 mmol) were added to a 10 L flask replaced with nitrogen , DMF (2.41 kg, 2.55 L) was further added to obtain a mixed solution. Thereafter, nitrogen gas (under nitrogen flow) was passed into the flask, while the flask was heated in an oil bath, and the above mixed solution was stirred for 30 minutes at 50-52° C. (o-tolyl) phosphine as a complex of palladium ligand. Then, for the mixed solution (yellow solution) containing the above-mentioned palladium complex, add 4-bromophthalic acid dimethyl ester (972 g, 3.56 mol, which is equivalent to the above-mentioned Compound (a kind of raw material compound) of the compound represented by the general formula (4)), dimethyl acetic acid dimethyl ester (680 g, 3.23 mol, is the compound (raw material) corresponding to the compound represented by the above general formula (5) One of the compounds)) to obtain a raw material mixture. Next, the temperature was raised to 80° C. while stirring the raw material mixed liquid obtained in this way.

On the other hand, triethylamine (655 g, 6.47 mol) and DMF (1.54 kg, 1.63 L) were added and mixed to another flask purged with nitrogen, and formic acid (298 g, 6.47 mol) was further added thereto , and fully mixed to room temperature (about 25° C.), thereby obtaining a mixed solution (A).

Then, the above-mentioned mixed solution (A) was added dropwise over 3 hours to the 10 L flask containing the raw material mixed solution heated to 80° C. in the above manner. In the step of dropping the mixed solution (A), the temperature of the oil bath is adjusted so that the temperature of the raw material mixed solution falls within the range of 78°C to 82°C, and the flask is heated in the oil bath. In this way, while the solution in the above-mentioned flask (the mixture of the above-mentioned raw material mixture and the above-mentioned mixture (A)) is fully stirred, the temperature of the solution is kept at 78°C to 82°C in the oil bath. It heated until 5 hours passed from the completion|finish of dripping of the said mixed liquid (A) (after the completion|finish of the dripping process of the mixed liquid (A)), and obtained the reaction liquid. In this way, after the dropwise addition of the mixed liquid (A) was completed, the flask was taken out from the oil bath after heating for 5 hours, and the reaction liquid was allowed to cool overnight (about 15 hours). Next, after adding water (4.2 L) to the obtained reaction liquid, it extracted twice with toluene (6.8 L), and obtained the toluene solution. Next, hydrochloric acid (HCl concentration: 5% by mass, 3.75 L), saturated sodium bicarbonate water (3.75 L), and water (3.75 L) were each used once in the order described, and the toluene solution was washed. Then, filter the remaining toluene solution with a filter covered with diatomaceous earth to remove black suspended matter in the toluene solution. Thereafter, the solvent was distilled off from the above-mentioned toluene solution to obtain 1414 g of a product containing a yellow oily substance.

For the product (oily substance) obtained in this way, GC analysis was carried out using the same conditions as <GC measurement condition 2> described in Example 1, and the quantification of PTBNE was carried out. The results can be seen from the results of GC analysis. The yield of PNBTE was 58.9%, and the content of PNBTE in the oily substance was 54.4% by mass.

(Example 4) After adding PNBTE (1.296 g, 3.205 mmol) obtained in Example 3 to a 50 mL flask with a reflux tube purged with nitrogen, acetic acid (18.0 g) was added to prepare an acetic acid solution. Next, after adding acetic anhydride (1.309 g, 12.82 mmol) to the above acetic acid solution, a solution obtained by dissolving TfOH (24.05 mg, 0.1602 mmol) in acetic acid (2.3 g) was added to prepare a mixed solution (containing PNBTE , acetic acid, acetic anhydride and TfOH mixture). Then, while passing nitrogen gas into the flask (under nitrogen flow), the flask was heated in an oil bath, and the above-mentioned mixed solution was refluxed for 9 hours (the above-mentioned mixed solution was heated under reflux conditions), thereby obtaining a reaction solution . From the reaction solution obtained in this way, by-product methyl acetate and acetic acid were distilled off under reduced pressure to obtain a product as a brown solid.

In order to confirm the structure of the product obtained in this way, NMR ( ¹ H-NMR, ¹³ C-NMR) measurement was performed. In the NMR measurement, an NMR measuring machine (manufactured by Varian, 600 MHz NMR) was used, and dimethylsulfoxide-D6 (DMSO-D6) was used as a solvent. That is, in order to confirm the structure of the product obtained in this manner, a part of the above product was sampled, adjusted by dilution with DMSO-D6, and NMR measurement was performed using the sample solution thus obtained.

From the measurement results of ¹ H NMR spectrum and ¹³ C NMR spectrum obtained in this way, it can be seen that the above product is a mixture of two compounds. That is, first, in the peak patterns of the ¹ H NMR spectrum and ^{the 13} C NMR spectrum, a peak pattern very consistent with ^{the 1} H NMR spectrum of PNBDA was confirmed, and thus it was judged that PNBDA was contained in the product. On the other hand, in the ¹ H NMR spectrum, two peaks of the proton of the methyl group of the methoxycarbonyl group were detected (3H was detected as a single peak at the position of 3.78 ppm, and further, a single peak was detected at the position of 3.79 ppm 3H) was detected, so it can be judged that 2 methoxycarbonyl groups in the 4 methoxycarbonyl groups of PNBTE have not reacted and the remaining compounds are also included in the product. Furthermore, in the ¹ H NMR spectrum, aromatic proton peaks were detected at positions of 7.50 ppm, 7.51 ppm and 7.69 ppm (1H was detected at 7.50 ppm, 1H was detected at 7.51 ppm, 1H was detected at 7.69 ppm 1H) was detected at the place, which is very consistent with the chemical shift of the aromatic proton of PNBTE, so it can be judged that the unreacted methoxycarbonyl group is two groups attached to the aromatic side. Also, in the peak pattern of the ¹³ C NMR spectrum, carbonyl carbon peaks were detected at 167.3 ppm and 168.0 ppm (1C was detected at 167.3 ppm, and 1C was detected at 168.0 ppm), which is consistent with the aroma of PNBTE The chemical shifts of the carbonyl carbon attached to the side of the group were very consistent, and another carbonyl carbon peak was detected at 173.3 ppm and 173.4 ppm (1C was detected at 173.3 ppm, and 1C was detected at 173.4 ppm), which It is very consistent with the chemical shift of the carbonyl carbon attached to the nor-alkane side of PNBDA, so it can be judged that the unreacted methoxycarbonyl is two groups attached to the aromatic side. From these results, it was confirmed that the above-mentioned product was a mixture of PNBDA and a compound represented by the following general formula (C).

[chemical 12]

Thus, in Example 4, it was confirmed from the result of NMR measurement that the compound represented by the said general formula (C) was produced. Furthermore, it can be seen from the integral value of the aromatic proton peak of ¹ H NMR that the obtained product is the ratio of the amount of substance between PNBDA and the compound represented by the above-mentioned general formula (C) ([PNBDA]: [Formula (C) Compound]) is a mixture formed by mixing the ratio of 1:2.

[Evaluation methods for properties of polyimide, etc.] Hereinafter, the evaluation method (measurement method) of the characteristic of the polyimide etc. obtained in each Example and each comparative example mentioned later is demonstrated. In addition, the IR measurement of polyimide used the FT-IR measuring machine (manufactured by Thermo Scientific, trade name: Nicolet iS10 FT-IR).

＜Measurement of turbidity (haze) and yellowness (YI)＞ The turbidity (HAZE: haze) and yellowness (YI) of polyimide obtained in each example etc. are obtained by directly using the film obtained in each example etc. as a sample for measurement, using Japanese The product name "Hazemeter NDH-5000" manufactured by Denshoku Industries Co., Ltd. or the product name "Spectrocolorimeter SD6000" manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measuring device, and the measurement was performed respectively to obtain the value. In addition, when performing this measurement, the turbidity (haze) was measured using a product name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. Meter SD6000" to measure the yellowness. Moreover, turbidity (haze) was calculated|required by measuring based on JISK7136 (issued in 2000), and yellowness (YI) was calculated|required by measuring based on ASTM E313-05 (issued in 2005). In addition, when YI is 20 or less and haze is 15 or less, it can be said that the coloring and turbidity of a film are little enough, and transparency is at a sufficiently high level.

<Determination of 1% weight loss temperature (Td1%) and 5% weight loss temperature (Td5%)> The 1% weight loss temperature and 5% weight loss temperature of the polyimide obtained in each Example etc. were measured in the following manner, respectively. That is, first, 2 to 4 mg of samples were prepared from the polyimide (film) obtained in each example, and the samples were placed in an aluminum sample pan, and a thermogravimetric analysis device (Seiko Denshi Electronics Co., Ltd.) was used. The product name "TG/DTA220" manufactured by Mi Technology Co., Ltd.) was used as a measuring device, and the temperature was raised from room temperature to 40°C while blowing nitrogen gas, and then 40°C was used as the starting temperature of the measurement, under the condition of a heating rate of 10°C/min It is obtained by measuring the temperature at which the weight of the sample used loses 1% and the temperature at which it loses 5% by heating.

＜Measurement of Glass Transition Temperature (Tg) and Coefficient of Linear Expansion (CTE)＞ First, test pieces with a size of 20 mm in length and 5 mm in width were cut out from the polyimide (film-like polyimide) obtained in each example, and used as measurement samples, and analyzed by thermomechanical analysis. A device (trade name "TMA8310" manufactured by RIGAKU) was used as a measuring device, and the TMA curve was obtained by performing measurement under the conditions of a tension mode (49 mN) and a heating rate of 5° C./min in a nitrogen atmosphere. Then, using the obtained TMA curve, with respect to the inflection point of the TMA curve caused by the glass transition, the curves before and after it were extrapolated, and the glass transition of the polyimide constituting the film obtained in each Example etc. was obtained. The value of temperature (Tg) (unit: °C). In addition, using the above TMA curve, calculate the average value of the change in length per 1°C within the temperature range of 100°C to 200°C, thereby calculating the coefficient of linear expansion (CTE) of polyimide (taking the obtained average value as the linear expansion coefficient of polyimide).

<Measuring method of dielectric loss tangent (tanδ) and relative permittivity (εr)> The determination of the value of dielectric loss tangent (tanδ) and relative permittivity (εr) is aimed at the polyimide (film) obtained in Example 5 and the polyimide (film) obtained in Comparative Example 1 conduct. When carrying out this measurement, cut out the sample piece of the size of width 1.5mm, length 70～80mm respectively from these polyimides (film), and make sample piece (thickness is directly adopted in each embodiment etc. Thickness of the obtained film) was measured using the resonant cavity perturbation method (according to IEC 62810) as the measurement method, and was measured as follows. That is, the measurement of the values of the dielectric loss tangent (tanδ) and the relative permittivity (εr) is to use the test piece (width: 1.5 mm, length: 70-80 mm, thickness: 17 μm) prepared in the above-mentioned manner. (Example 5) or 33 μm (Comparative Example 1)) were left at 23°C for 24 hours in an environment with a relative humidity of 50%, and then carried out in a laboratory adjusted to an environment of 23°C and a relative humidity of 50%. Also, as a measuring device, "PNA Network Analyzer N522B" manufactured by Keysight Technologies Co., Ltd. and "CP531 for cavity resonator 10 GHz" manufactured by Kanto Electronics Application Development Co., Ltd. were used. In the measurement, the above-mentioned test piece was installed in the cavity resonator of the above-mentioned measuring device, the frequency was set to 10 GHz, and the actual measured values of dielectric loss tangent (tanδ) and relative permittivity (εr) were obtained respectively. Then, the measurement of such measured values was carried out twice in total, and the average value thereof was obtained to obtain the values of dielectric loss tangent (tanδ) and relative permittivity (εr). In this way, as the values of the dielectric loss tangent (tanδ) and the relative permittivity (εr), the average value of the actually measured values obtained by the two measurements was adopted.

＜Determination of intrinsic viscosity [η]＞ Regarding the intrinsic viscosity [η] of polyamic acid or polyimide, the solvent used in the preparation of the reaction solution (resin solution: polyimide solution or polyamic acid solution) in each example was used as the dilution Solvent, prepare a solution of polyamic acid or polyimide with a concentration of 0.5 g/dL as a measurement sample, and use an automatic viscosity measuring device (trade name "miniPV (registered trademark)-HX") manufactured by CANNON INSTRUMENT COMPANY as The measurement device is used for measurement at a temperature of 30°C.

(Example 5) First, the atmosphere in a 50 mL two-necked flask was replaced with nitrogen, so that the above-mentioned two-necked flask was a nitrogen atmosphere. Then, under a nitrogen atmosphere, 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (TFMB) 1.0275 g ( 3.209 mmol), PNBDA obtained in Example 2 (tetracarboxylic dianhydride represented by the above formula (B)) 1.0020 g (3.209 mmol). Then, 6.089 g of a mixed solvent of N,N-dimethylacetamide (DMAc) and γ-butyrolactone (GBL) (mass ratio: DMAc/GBL=1/1) was added to the above-mentioned two-necked flask, and at the same time 16.2 mg (0.160 mmol) of triethylamine was added and stirred to obtain a mixed liquid.

Next, while passing nitrogen gas into the above-mentioned two-necked flask (under a nitrogen gas flow), the obtained mixed liquid was heated and stirred at 180° C. for 5 hours, thereby obtaining a reaction liquid. Furthermore, the heating and stirring step of this kind of mixed solution is to distill off the water and solvent (DMAc) produced in the heating process together, and add DMAc in the same amount as the distilled solvent (DMAc) to the above two ports. inside the flask. Furthermore, considering the types of the functional group (amine group) of TFMB and the functional group (carboxylic acid anhydride group) of PNBDA, as well as the above-mentioned heating temperature (180°C), it is obvious that it is formed in the above-mentioned mixed solution by the above-mentioned heating and stirring step. It is obvious that the above reaction solution is a solution of polyimide (solvent: DMAc and GBL). Also, after isolating polyimide by using a part of the reaction solution (polyimide solution), a DMAc solution having a polyimide concentration of 0.5 g/dL was prepared as a measurement sample, and the concentration of polyimide was measured. Intrinsic viscosity [η], the result is that the intrinsic viscosity [η] of polyimide is 0.34 dL/g. In addition, the measurement method is as follows.

Next, directly using the above-mentioned reaction liquid as a coating liquid, the above-mentioned coating liquid (the above-mentioned reaction liquid) was spin-coated on a glass plate (76 mm in length, 52 m in width, and 1.3 mm in thickness) to form a coating film. Then, put the glass plate formed with the above-mentioned coating film into a vacuum thermal chamber, and let it stand for 1 hour under the conditions of a nitrogen atmosphere, a pressure of about 100 Pa, and a temperature of 70°C. In this way, a dry coating film of polyimide was formed on the glass substrate. Then, the glass plate formed with the above-mentioned dry coating film was put into a non-oxidizing oven, and in the non-oxidizing oven, under a nitrogen atmosphere, the temperature was raised from 30°C to 350°C at a rate of 4°C/min, and then the temperature was increased from 350°C to 350°C. The firing temperature was maintained for 60 minutes, thereby firing the above-mentioned dried coating film, and then slowly cooling to room temperature in about 6 hours, thereby forming a film comprising polyimide (polyimide) on the above-mentioned glass substrate. imide film). Next, the glass plate on which the film was formed was taken out of the oven, and immersed in water at 90° C. for 0.5 hour to peel off the polyimide film from the glass substrate and recover the polyimide film. In this way, a polyimide-containing film (length 76 mm, width 52 mm, thickness 17 μm) was obtained.

The IR spectrum of the film obtained in this way was measured. In addition, the measurement of IR spectrum used the FT-IR measuring machine (manufactured by Thermo Scientific, trade name: Nicolet iS10 FT-IR). The IR spectrum of the obtained film is shown in FIG. 6 . It is also clear from the results shown in Fig. 6 that the C=O stretching vibration of the imide carbonyl group was observed at 1714 cm ^-1 , thus confirming that the obtained film contains polyimide.

(comparative example 1) The amount of TFMB used was changed from 1.0275 g (3.209 mmol) to 6.4046 g (20.000 mmol), and 8.1286 g (20.000 mmol) of tetracarboxylic dianhydride (BzDA) represented by the following formula (D) was used instead of PNBDA. 10.9 g (mass ratio: NMP/GBL=1/1) of the mixed solvent of N-methyl-2-pyrrolidone (NMP) and GBL is used to replace the mixed solvent of DMAc and GBL, and in order to obtain the reaction solution (polyamide amine solution), the above-mentioned mixed solution was heated and stirred at 180°C for 6 hours instead of the above-mentioned mixed solution was heated and stirred at 180°C for 5 hours. The film (length 76 mm, width 52 mm, thickness 33 μm).

[chemical 13]

Furthermore, BzDA was synthesized using the method described in Example 1 of International Publication No. 2015/163314.

[About the characteristics of the polyimide obtained in Example 5 and Comparative Example 1] Since the types of diamine compounds used to prepare polyimides are all TFMB, in order to evaluate the differences in the properties of polyimides based on the differences in the types of tetracarboxylic dianhydrides, the results obtained in Example 5 and Comparative Example 1 were compared. For polyimide, use the above measurement methods to evaluate the characteristics (YI, HAZE, Tg, Td5%, Td1%, CTE, relative permittivity, dielectric loss tangent). The obtained results are shown in Table 1.

[Table 1] Raw material compounds and preparation conditions for the production of polyimide Properties of polyimide Tetracarboxylic dianhydride Diamine compound Intrinsic Viscosity ^(*1) (dL/g) Roasting conditions Film thickness (μm) YI HAZE Tg, (℃) Td5% (℃) Td1% (℃) CTE, (ppm/K) Relative permittivity (10 GHz) Dielectric Loss Tangent (10 GHz) Example 5 PNBDA TFMB 0.34 350°C, 60 minutes 17 3.3 0.7 395 486 457 47 2.71 0.0161 Comparative example 1 BYZGR TFMB 0.32 350°C, 60 minutes 33 1.9 1.0 341 481 444 68 2.96 0.0181 (*1) Intrinsic viscosity of polyimide solution

It is also clear from the results shown in Table 1 that the polyimides obtained in Example 5 and Comparative Example 1 all satisfy the conditions of Td1% being 420°C or higher and Td5% being 470°C or higher. The heat resistance based on (Td1%, Td5%) is at a sufficiently high level. In addition, the polyimides obtained in Example 5 and Comparative Example 1 all satisfied the conditions of YI being 20 or less and HAZE being 15 or less, and it was also confirmed that the coloring and turbidity of the film were sufficiently low and the transparency was sufficiently high. level. Furthermore, as is clear from the values of YI and HAZE shown in Table 1, the polyimide obtained in Example 5 is more excellent in transparency than the conventional aromatic polyimide.

Here, it is also clear from the results shown in Table 1 that when using PNBDA as tetracarboxylic dianhydride to manufacture polyimide (Example 5), Tg, Td1%, Td5% are the same as using BzDA as tetracarboxylic dianhydride. Compared with the case of producing polyimide with acid dianhydride (Comparative Example 1), all of them have more excellent values. From this, it was confirmed that in the case of producing polyimide using the same diamine compound (TFMB), In the case of using PNBDA, a higher level of heat resistance was obtained than in the case of using BzDA. Also, in the case of using PNBDA to produce polyimide (Example 5), compared with the case of using BzDA to produce polyimide (Comparative Example 1), the CTE is a lower value. When the polyimide is prepared from the same diamine compound (TFMB), the CTE can be made lower in the case of using PNBDA than in the case of using BzDA. Furthermore, from the measurement results of relative permittivity and dielectric loss tangent, it can be seen that when using the same diamine compound (TFMB) to prepare polyimide, the situation of using PNBDA is relatively lower than that of using BzDA. The dielectric constant and dielectric loss tangent are lower values. From these results, it was confirmed that the polyimide of the present invention can make the yellowness and turbidity lower than a certain level, and the heat resistance can be made higher, and furthermore, the linear expansion can be improved. The coefficient is a lower value (in other words, it is confirmed from this result that when the tetracarboxylic dianhydride of the present invention (PNBDA obtained in Example 2) is used as a raw material monomer for producing polyimide , the yellowness and turbidity of the obtained polyimide can be lowered below a certain level, and the heat resistance can be made higher, and the linear expansion coefficient can also be lowered).

(Example 6) Under a nitrogen atmosphere, introduce 0.2562 g (1.279 mmol) of 4,4'-diaminodiphenyl ether (4,4'-DDE), N,N-dimethylacetamide ( DMAc) 3.6960 g. Then, 0.4002 g (1.282 mmol) of PNBDA (tetracarboxylic dianhydride represented by said formula (B)) was added in the said spiral tube, and the liquid mixture was obtained. Next, the obtained mixed solution was stirred at room temperature (about 25° C.) for 2 days in a nitrogen atmosphere to obtain a reaction solution. In this way, polyamic acid is formed in the reaction liquid. Furthermore, using a part of the reaction solution (the DMAc solution of polyamic acid) obtained in this way, a DMAc solution with a concentration of 0.5 g/dL of polyamic acid was prepared, and the intrinsic viscosity [η ], the result is that the intrinsic viscosity [η] of polyamic acid is 0.61 dL/g.

Then, put the glass plate with the above-mentioned coating film into the vacuum thermal chamber, and let it stand for 1 hour under the conditions of nitrogen atmosphere, pressure of about 100 Pa, and temperature of 70°C. In this way, a dry coating film of polyamic acid was formed on the glass substrate. Then, the glass plate formed with the above-mentioned dry coating film was put into a non-oxidizing oven, and in the non-oxidizing oven, under a nitrogen atmosphere, the temperature was raised from 30°C to 350°C at a rate of 4°C/min, and then the temperature was increased from 350°C to 350°C. The firing temperature was maintained for 10 minutes, thereby firing the above-mentioned dry coating film, and then slowly cooling to room temperature in about 6 hours, thereby forming a film containing polyimide (polyamide) on the above-mentioned glass substrate. imine film). Next, the glass plate on which the film was formed was taken out of the oven, and immersed in water at 90° C. for 0.5 hour to peel off the polyimide film from the glass substrate and recover the polyimide film. In this way, a polyimide-containing film (length 76 mm, width 52 mm, thickness 17 μm) was obtained.

The IR spectrum of the film obtained in this way was measured. The IR spectrum of the obtained film is shown in FIG. 7 . It is also clear from the results shown in Fig. 7 that the C=O stretching vibration of the imide carbonyl group was observed at 1705 cm ^-1 , thus confirming that the obtained film contains polyimide.

(Example 7) The amount of PNBDA used was changed from 0.2562 g to 1.022 g (3.273 mmol), and 0.7438 g (3.273 mmol) of 4,4'-diaminobenzamide aniline (DABAN) was used instead of 4,4' -DDE, use 7.077 g of tetramethylurea (N,N,N',N'-tetramethylurea: TMU) instead of DMAc, change the stirring time of the mixed solution from 2 days to 4 days when obtaining the reaction solution, Except for this, a polyimide-containing film (length 76 mm, width 52 mm, thickness 16 μm) was obtained in the same manner as in Example 6. Furthermore, the intrinsic viscosity [η] of polyamic acid was measured in the same manner as in Example 6. As a result, the intrinsic viscosity [η] of polyamic acid was 0.38 dL/g. Also, the IR spectrum of the film obtained in this way was measured. The IR spectrum of the obtained film is shown in FIG. 8 . It is also clear from the results shown in Fig. 8 that the C=O stretching vibration of the imide carbonyl group was observed at 1703 cm ^-1 , thus confirming that the obtained film contains polyimide.

(Example 8) The amount of PNBDA used was changed from 0.2562 g to 1.0123 g (3.242 mmol), and 2,2'-dimethyl-[1,1'-biphenyl]-4,4'-diamine ( MTD) 0.6891 g (3.246 mmol) to replace 4,4'-DDE, change the amount of DMAc used from 3.6960 g to 3.9696 g, change the stirring time of the mixed solution from 2 days to 3 days when obtaining the reaction solution, and change In the non-oxidizing oven, the heating rate from 30°C to 350°C was changed to 2°C/min. Except that, a film (76 mm in length, 52 mm in width) comprising polyimide was obtained in the same manner as in Example 6. mm, thickness 13 μm). Furthermore, the intrinsic viscosity [η] of polyamic acid was measured in the same manner as in Example 6. As a result, the intrinsic viscosity [η] of polyamic acid was 0.35 dL/g. Also, the IR spectrum of the film obtained in this way was measured. The IR spectrum of the obtained film is shown in FIG. 9 . It is also clear from the results shown in Fig. 9 that the C=O stretching vibration of the imide carbonyl group was observed at 1706 cm ^-1 , thus confirming that the obtained film contains polyimide.

(Example 9) Change the usage amount of PNBDA from 0.2562 g to 1.099 g (3.519 mmol), use p-phenylenediamine (PPD) 0.3804 g (3.518 mmol) instead of 4,4'-DDE, use TMU 8.3838 g to Instead of DMAc, the stirring time of the mixed solution when obtaining the reaction solution was changed from 2 days to 3 days, and the temperature increase rate when the temperature was raised from 30°C to 350°C in the non-oxidizing oven was changed to 2°C/min. In addition, A polyimide-containing film (length 76 mm, width 52 mm, thickness 13 μm) was obtained in the same manner as in Example 6. Furthermore, the intrinsic viscosity [η] of polyamic acid was measured in the same manner as in Example 6. As a result, the intrinsic viscosity [η] of polyamic acid was 0.31 dL/g. Also, the IR spectrum of the film obtained in this way was measured. The IR spectrum of the obtained film is shown in FIG. 10 . It is also clear from the results shown in Fig. 10 that the C=O stretching vibration of the imide carbonyl group was observed at 1704 cm ^-1 , thus confirming that the obtained film contains polyimide.

(Example 10) The amount of PNBDA was changed from 1.0020 g to 0.9637 g (3.086 mmol), and a mixture of 4,4'-(9H-fennel-9,9-diyl)diphenylamine (FDA) and DABAN was used to Instead of TFMB, set the usage amount of FDA to 0.5377 g (1.543 mmol), set the usage amount of DABAN to 0.3507 g (1.543 mmol), changed the usage amount of triethylamine to 15.6 mg (0.154 mmol), and changed the mixed solvent The amount used was changed from 6.089 g to 5.556 g, the roasting temperature in the non-oxidizing oven was changed from 350°C to 300°C, and the temperature in the non-oxidizing oven was raised from 30°C to 300°C instead of from 30°C to 350°C, and In the non-oxidizing oven, the time maintained at the firing temperature was changed from 60 minutes to 120 minutes. In addition, a film (76 mm in length, 52 mm in width, thickness 20 μm). The IR spectrum of the film obtained in this way was measured. The IR spectrum of the obtained film is shown in FIG. 11 . It is also clear from the results shown in Fig. 11 that the C=O stretching vibration of the imide carbonyl group was observed at 1706 cm ^-1 , thus confirming that the obtained film contains polyimide.

(Example 11) Change the amount of PNBDA from 1.0020 g to 0.952 g (3.094 mmol), use a mixture of TFMB and MTD instead of TFMB, set the amount of TFMB to 0.4881 (1.524 mmol), and change the amount of MTD Set it to 0.3236 g (1.524 mmol), change the usage amount of triethylamine to 15.4 mg (0.152 mmol), change the usage amount of mixed solvent from 6.089 g to 5.291 g, and heat and stir the mixture at 180°C The time was changed from 5 hours to 4 hours, the calcination temperature in the non-oxidizing oven was changed from 350°C to 300°C, and the temperature in the non-oxidizing oven was raised from 30°C to 300°C instead of from 30°C to 350°C, and the In the non-oxidizing oven, the time maintained at the firing temperature was changed from 60 minutes to 120 minutes. Except that, a film (76 mm in length, 52 mm in width, and 29 mm in thickness) comprising polyimide was obtained in the same manner as in Example 5. μm). The IR spectrum of the film obtained in this way was measured. The IR spectrum of the obtained film is shown in FIG. 12 . It is also clear from the results shown in Fig. 12 that the C=O stretching vibration of the imide carbonyl group was observed at 1709 cm ^-1 , thus confirming that the obtained film contains polyimide.

[About the characteristics of the polyimides obtained in Examples 6 to 11] Table 2 shows the evaluation results of the properties (film thickness, YI, HAZE, Tg, Td5%, Td1%, and CTE) of the polyimides obtained in Examples 6 to 11, respectively. In addition, "-" in Table 2 means not measured.

[Table 2] Raw material compounds and preparation conditions for the production of polyimide Properties of polyimide Tetracarboxylic dianhydride Diamine compound Intrinsic Viscosity ^(*1) (dL/g) Roasting conditions Film thickness (μm) YI HAZE Tg, (℃) Td5% (℃) Td1% (℃) CTE (ppm/K) Example 6 PNBDA 4,4'-DDE 0.61 350°C, 10 minutes 17 5.2 0.5 338 481 454 55 Example 7 PNBDA DABAN 0.38 350°C, 10 minutes 16 6.3 0.3 389 479 427 56 Example 8 PNBDA MTD 0.35 350°C, 10 minutes 13 4.4 1.6 356 479 444 69 Example 9 PNBDA PPD 0.31 350°C, 10 minutes 13 6.0 0.3 407 490 446 57 Example 10 PNBDA FDA＋DABAN - 300°C, 120 minutes 20 3.3 0.6 412 482 460 54 Example 11 PNBDA TFMB+MTD - 300°C, 120 minutes 29 2.0 1.1 391 477 458 61 (*1) Intrinsic viscosity of polyamic acid solution

It is also clear from the results shown in Table 2 that the polyimides obtained in Examples 6 to 11 all satisfy the conditions that Td1% is 420°C or higher and Td5% is 470°C or higher, and it was confirmed that the weight loss temperature (Td1 %, Td5%) as the benchmark heat resistance is at a sufficiently high level. In addition, the polyimides obtained in Examples 6 to 11 all satisfied the conditions of YI being 20 or less and HAZE being 15 or less. From this, it was also confirmed that the coloring or turbidity of the film was sufficiently low, and the transparency was at a sufficiently high level. . Furthermore, it is clear from the values of YI and HAZE shown in Table 2 that the polyimides obtained in Examples 6 to 11 are more transparent than the previous aromatic polyimides. excellent.

Considering the results shown in Table 1 and Table 2 together, it can be seen that the polyimide of the present invention can make yellowness and turbidity lower than a certain level, and can make heat resistance higher. Also, it can be seen that the polyimide according to the present invention has lower values of CTE, relative permittivity, and dielectric loss tangent than the case of producing polyimide using BzDA (Comparative Example 1). [Industrial availability]

As described above, according to the present invention, when used as a raw material monomer for producing polyimide, the yellowness and turbidity of the obtained polyimide can be provided below a certain level. A tetracarboxylic dianhydride that has a lower value and can make heat resistance higher; a carbonyl compound that can be used as a raw material for efficiently producing the tetracarboxylic dianhydride; the above-mentioned tetracarboxylic dianhydride can be used A compound containing an acid anhydride group obtained in the form of an intermediate; a production method capable of efficiently and reliably producing the above-mentioned tetracarboxylic dianhydride; and a production method capable of efficiently and reliably producing the above-mentioned carbonyl compound. Such tetracarboxylic dianhydrides of the present invention can be preferably used as monomers for forming polymers (more preferably polyimides), epoxy hardeners, raw materials for pharmaceuticals, and the like based on their structures.

Also, according to the present invention, it is possible to provide a polyimide that can make the yellowness and turbidity lower than a certain level and can make the heat resistance higher, and can be preferably used for the production of the polyimide. Polyimide precursor resin of imide. Such polyimide of the present invention can be suitably used in films for flexible wiring boards, films for liquid crystal alignment films, transparent conductive films for organic EL (Electroluminescence, electroluminescence), and films for organic EL lighting , Flexible substrate film, flexible organic EL substrate film, flexible transparent conductive film, transparent conductive film, transparent conductive film for organic thin-film solar cells, transparent conductive film for dye-sensitized solar cells, flexible gas barrier film , Films for touch panels, front films for flexible displays, back films for flexible displays, polyimide tapes, coating agents, barrier films, sealing materials, interlayer insulating materials, passivation films, TAB (Tape Automated Bonding, Tape type automatic bonding) tape, FPC (Flexible Print Circuit, flexible printed circuit board), COF (Chip On Film, film on chip), optical waveguide, color filter substrate, semiconductor coating agent, heat-resistant insulating tape, Enameled wire paint and other uses.

Fig. 1 is a graph showing the relationship between the number of measurements and the results of thin-layer chromatography (TLC) measurements of eluate derived from silica gel flash column chromatography. FIG. 2 is a graph showing the ¹ H NMR spectrum of the tetraester compound PNBTE obtained in Example 1. FIG. FIG. 3 is a graph showing the ¹³ C NMR spectrum of the tetraester compound PNBTE obtained in Example 1. FIG. FIG. 4 is a graph showing the ¹ H NMR spectrum of tetracarboxylic anhydride PNBDA obtained in Example 2. FIG. FIG. 5 is a graph showing the ¹³ C NMR spectrum of tetracarboxylic anhydride PNBDA obtained in Example 2. FIG. FIG. 6 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 5. FIG. FIG. 7 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 6. FIG. FIG. 8 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 7. FIG. FIG. 9 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 8. FIG. FIG. 10 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 9. FIG. FIG. 11 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 10. FIG. FIG. 12 is a graph of the infrared absorption spectrum (IR spectrum) of the polyimide obtained in Example 11. FIG.

Claims (7)

A tetracarboxylic dianhydride represented by the following general formula (1): [Chem. 1]

[In formula (1), R ¹ to R ⁵ each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms]. A carbonyl compound represented by the following general formula (2): [Chem. 2]

[In formula (2), R ¹ to R ⁵ independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁶ and R ⁷ independently represent a group selected from a hydrogen atom and one of the group consisting of hydrocarbon groups with 1 to 10 carbon atoms]. A compound containing an acid anhydride group represented by the following general formula (3): [Chemical 3]

[In formula (3), R ¹ to R ⁵ independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁶ independently represent a group selected from a hydrogen atom and a carbon number One of the group consisting of 1 to 10 hydrocarbon groups]. A kind of manufacture method of tetracarboxylic dianhydride, it is by using acid catalyst, carbonyl compound represented by following general formula (2) is heated in the carboxylic acid of carbon number 1～5, and obtains following general Tetracarboxylic dianhydride represented by formula (1), [Chem. 4]

[In formula (2), R ¹ to R ⁵ independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁶ and R ⁷ independently represent a group selected from a hydrogen atom and one of the group consisting of hydrocarbon groups with 1 to 10 carbons] [Chemical 5]

[In formula (1), R ¹ to R ⁵ each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms]. A method for producing a carbonyl compound, which is to make the following general formula ( 4) The aromatic compound represented by the following general formula (5) reacts with the alicyclic compound represented by the following general formula (5), and the carbonyl compound represented by the following general formula (2) is obtained, [Chemical 6]

[In formula (4), R ¹ to R ³ independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbons, and R ⁶ independently represent one selected from the group consisting of 1 to 10 carbons. One of the group consisting of hydrocarbon groups, X represents a halogen atom] [Chemical 7]

[In formula (5), R ⁴ to R ⁵ independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁷ independently represent one selected from the group consisting of 1 to 10 carbons One of the group consisting of hydrocarbon groups] [Chemical 8]

[In formula (2), R ¹ to R ⁵ independently represent one type selected from the group consisting of a hydrogen atom and a hydrocarbon group with 1 to 20 carbons, and R ⁶ and R ⁷ independently represent a group selected from a hydrogen atom and one of the group consisting of hydrocarbon groups with 1 to 10 carbon atoms]. A polyimide comprising a polycondensate of a monomer (A) and a monomer (B) as a diamine compound, the monomer (A) comprising tetracarboxylic acids represented by the following general formula (1) At least one compound of the group consisting of dianhydrides and their derivatives, [化9]

[In formula (1), R ¹ to R ⁵ each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms]. A polyimide precursor comprising a polyadduct of a monomer (A) and a monomer (B) as a diamine compound, the monomer (A) comprising: At least one compound of the group consisting of tetracarboxylic dianhydrides and derivatives thereof, [Chem. 10]

[In formula (1), R ¹ to R ⁵ each independently represent one species selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms].

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