JP5315496B2 - Novel (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride having high polymerization capability as a raw material of a polyimide. <P>SOLUTION: The compound 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride is subjected to selective isomerization and to anhydride formation to obtain new (1S,2S,4R,5R)-cyclohexane tetracarboxylic acid dianhydride. The anhydride makes a high-molecular weight substance of a polyimide precursor easily obtainable by being reacted with various diamines. Further, the polyimide obtained by imidization fulfills strikingly high transparency, high heat resistance, sufficient film toughness and very low permittivity. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention has high transparency, sufficient film toughness, low dielectric constant, and high glass transition temperature. Electrical insulating films, liquid crystal display (LCD) substrates, organic electroluminescence (EL) display substrates, and electronic devices in various electronic devices. Paper substrate, solar cell substrate, semiconductor element interlayer insulating film and protective film, liquid crystal alignment film, optical waveguide material, especially display substrate, semiconductor element interlayer insulating film and protective film, polyimide useful as liquid crystal alignment film The novel (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, its tetracarboxylic acid, its production method, its polyimide precursor, its polyimide, and the use of the polymer as its precursor monomer Is.

  1,2,4,5-Cyclohexanetetracarboxylic acid and its dianhydride are useful compounds as raw materials for high heat resistance, high transparency, low dielectric constant, and high toughness polyimide (see, for example, Patent Document 1).

  Conventionally, as a method for producing 1,2,4,5-cyclohexanetetracarboxylic acid, a method of hydroreducing the benzene ring of pyromellitic acid ester (see, for example, Patent Document 2 and Non-Patent Document 1), pyromellitic acid A method for directly hydroreducing a benzene ring (for example, see Patent Document 3 and Non-Patent Document 2) has been reported.

  However, the dianhydride of 1,2,4,5-cyclohexanetetracarboxylic acid synthesized by these methods is inferior in polymerization reactivity with diamine and does not reach a sufficient degree of polymerization, so that it exhibits a sufficient film toughness. Molecular weight products are often not obtained. This is because 1,2,4,5-cyclohexanetetracarboxylic dianhydride is represented by the following formulas (6) and (7):

(In formula (6), B represents a tetravalent ship-type cyclohexane group, and the configuration thereof is represented by the following formula (7).)

(The carbonyl group at the 1,2-position is a cis-isomer in the same direction, the 4,5-position is also a cis-isomer, and the 1,2-position and the 4,5-position are the same.) It is considered that it is a cis isomer facing in the direction) and has a thermodynamically most stable three-dimensional structure (for example, see Non-Patent Document 3). In addition, 1,2,4,5-cyclohexanetetracarboxylic dianhydride may cause steric hindrance during the polymerization reaction due to the spatial proximity of the functional acid anhydride groups. This is also considered to contribute to the low polymerization reactivity.

Thus, it is not easy to obtain a transparent and tough polyimide film using 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and a material that satisfies the required characteristics as a plastic substrate for flexible displays. Is also unknown.
JP 2003-168800 A (published on June 13, 2003) JP-A-8-325196 (released on December 10, 1996) JP 2003-286222 A (released on October 10, 2003) Dnaiel T. Longone, Derivatives of Pyromellitic Acid. 1,2,4,5-Tetrasubstituted Cyclohexanes, J. Org. Chem., 1963, vol.28, pp1770-1773 Morris Freifelder, Daniel A. Dunnigan, and Evelyn J. Baker, Low-Pressure Hydrogenation of Some Benzenepolycarboxylic Acids with Rhodium Catalyst, J. Org. Chem., 1966, vol.31, pp3438-3439 Higher Performace Polymers. 2007, vol. 19, p175

  Even if 1,2,4,5-cyclohexanetetracarboxylic acid obtained by conventional techniques is anhydrideized, its reactivity with diamine is low compared to aromatic compounds such as pyromellitic dianhydride. It was difficult to produce a high polyimide precursor (polyamic acid). It has been clarified that polyimides having a 1,2,4,5-cyclohexanetetracarboxylic acid block have excellent properties such as high transparency and low dielectric constant, but the problem of low polymerizability as described above. Development was difficult due to the main reason.

  The present invention has been made to overcome such problems, and its purpose is to combine high transparency, sufficient film toughness, low dielectric constant, and high glass transition temperature, and various electric insulations in various electronic devices. Film and liquid crystal display (LCD) substrates, organic electroluminescence (EL) display substrates, electronic paper substrates, solar cell substrates, interlayer insulation films and protective films for semiconductor elements, liquid crystal alignment films, optical waveguide materials, especially displays A novel 1,2,4,5-cyclohexanetetracarboxylic acid useful as a raw material of polyimide useful as a substrate, interlayer insulating film and protective film for semiconductor elements, and liquid crystal alignment film, and a technology using the same There is.

  In view of the above problems, the inventors have conducted extensive research, and as a result, in order to precisely control the three-dimensional structure of 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, which has poor conventional polymerization reactivity, this tetra The following general formula (8) is obtained by selectively isomerizing the carboxylic acid and making it anhydrous.

(In formula (8), X represents a tetravalent cyclohexane group, and the configuration is represented by the following formula (2).)

A novel (1S, 2S, 4R, 5R) -tetracarboxylic dianhydride (hereinafter referred to as tt-CHTCA) represented by the formula (7): It has been found that a isomer of 2,4,5-cyclohexanetetracarboxylic dianhydride can be produced.

  In addition, by using this tt-CHTCA, it is possible to easily obtain a high molecular weight polymer of a polyimide precursor by reacting with various diamines, and the polyimide obtained by imidizing it is extremely high in transparency and high. Because it achieves heat resistance, sufficient film toughness, and extremely low dielectric constant, it can provide unprecedented useful materials such as plastic substrates for flexible liquid crystal displays, interlayer insulating films of integrated circuits, and liquid crystal alignment films As a result, the present invention has been completed.

That is, the present invention includes the following inventions.
(1) tt-CHTCA.
(2) 1,2,4,5-cyclohexanetetracarboxylic dianhydride characterized by containing 50% or more of tt-CHTCA.
(3) (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid (hereinafter referred to as “tt-CHTC”).
(4) cis-cis-cis isomer of 1,2,4,5-cyclohexanetetracarboxylic acid (hereinafter referred to as “cis-CHTC”, and the cis-CHTC anhydride is referred to as “cis-CHTCA”) And a method for producing tt-CHTC, wherein at least one of the tetra-salts in the mixture of isomers is subjected to an isomerization reaction by heating.
(5) A method for producing tt-CHTC, characterized in that at least one tetraester of cis-CHTC and an isomer mixture containing the cis-CHTC is subjected to an isomerization reaction by heating.

According to this production method, the reaction can be carried out from a cis-CHTC tetraester that is relatively unstable to heat even at a relatively low temperature. This isomerization reaction may be promoted by a catalyst.
(6) The method for producing tt-CHTC according to (4), wherein a basic catalyst is used in the isomerization reaction.
(7) The method for producing tt-CHTC according to (6), wherein an alkali metal alkoxide is used as the basic catalyst.
(8) A process for producing tt-CHTCA tetracarboxylic dianhydride, comprising a step of dehydration reaction by heating tt-CHTC in the presence of a dehydrating agent.
(9) A method for producing tetracarboxylic dianhydride, comprising a step of dehydration reaction by heating tt-CHTC in the presence of a dehydrating agent.
(10) A tetracarboxylic dianhydride produced by the production method according to (9).
(11) General formula (1)

(In the above general formula (1), X represents a tetravalent cyclohexane group, and R represents a hydrogen atom, a trialkylsilyl group, or a linear, branched or cyclic alkyl group or alkoxyl group having 1 to 12 carbon atoms. A represents a divalent aromatic group or aliphatic group, and the configuration of X is represented by the following formula (2):

The bonding position between the X and the two amide groups and two carboxyl groups bonded to the X is represented by either the following formula (3) or (4).

(In formulas (3) and (4), Y represents two amide groups bonded to X, and Z represents two carboxyl groups bonded to X))
The polyimide precursor which has a repeating unit represented by these.
(12) The following general formula (5)

(In formula (5), X represents a tetravalent cyclohexane group, A represents a divalent aromatic group or an aliphatic group, and the configuration of X is represented by the following formula (2)).

The polyimide which has a repeating unit represented by these.
(13) A polyimide precursor obtained using 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a synthesis raw material, wherein the 1,2,4,5-cyclohexanetetracarboxylic dianhydride is (10 50) or more of the tetracarboxylic dianhydride described in 1).
(14) A polyimide obtained using 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a synthesis raw material, wherein the 1,2,4,5-cyclohexanetetracarboxylic dianhydride is converted to (10) A polyimide comprising 50% or more of the tetracarboxylic dianhydride described.
(15) A photosensitive resin composition comprising the polyimide precursor according to (11) or (13) and a photosensitive agent.
(16) The photosensitive resin composition according to (15) is subjected to pattern exposure on a substrate, developed after pattern exposure, and heat-cured after development to form a pattern. A structure characterized by that.
(17) A substrate for display comprising the polyimide according to (12) or (14).
(18) An interlayer insulating film for an integrated circuit comprising the polyimide according to (12) or (14).
(19) A liquid crystal alignment film containing the polyimide according to (12) or (14).

  According to the present invention, it has high transparency, sufficient film toughness, low dielectric constant, and high glass transition temperature, and each electric insulating film and liquid crystal display (LCD) substrate in various electronic devices, organic electroluminescence (EL) display. Substrates, electronic paper substrates, solar cell substrates, interlayer insulating films and protective films for semiconductor elements, liquid crystal alignment films, optical waveguide materials, especially display substrates, interlayer insulating films and protective films for semiconductor elements, and liquid crystal alignment films A novel 1,2,4,5-cyclohexanetetracarboxylic acid useful as a useful polyimide raw material can be provided.

  That is, a high-molecular-weight polyimide precursor that could not be obtained using conventional cis-CHTCA by using extremely high-purity tt-CHTCA synthesized as a monomer according to the method for producing tt-CHTCA according to the present invention. Body and high molecular weight polyimide can be easily manufactured. As a result, the brittleness of the polyimide film is greatly improved, and it is possible to provide extremely useful materials in various industries related to the above-mentioned electronic devices and the like. .

  An embodiment of the present invention will be described as follows, but the present invention is not limited to this. The scope of the present invention is not limited by these descriptions, and other than the following examples, the scope of the present invention can be appropriately modified and implemented without departing from the scope of the present invention.

<1. tt-CHTC and tt-CHTCA>
Tt-CHTC according to the present invention is a compound represented by the following formula (8).

(In formula (8), X represents a tetravalent cyclohexane group, and its steric configuration is represented by the following formula (2). In other words, it may be referred to as a tetravalent chair-type cyclohexane group.)

Moreover, tt-CHTCA according to the present invention is a compound represented by the following formula (9), and can be obtained, for example, by anhydrating tt-CHTC.

(In formula (9), X is the same as that in formula (8).)
The tt-CHTCA according to the present invention has extremely high polymerizability and is extremely useful as a polyimide monomer. When reacted with various diamines in N, N-dimethylacetamide (DMAc) or N-methyl-2-pyrrolidone (NMP), the intrinsic viscosity of the resulting polyamic acid solution was measured, and the polymerizability was evaluated. In the case of using tt-CHTCA according to the above, the intrinsic viscosity of the polyamic acid is 0.65 to 2.4 dL / g. This is an extremely high value as compared with the polymerizability of CHTCA that has been conventionally used, usually 0.1 to 0.5 dL / g, and a polyimide having a high degree of polymerization can be easily produced.

  Moreover, the 1,2,4,5-cyclohexanetetracarboxylic dianhydride according to the present invention contains 50% or more of tt-CHTCA. By containing 50% or more of tt-CHTCA useful as a polyimide monomer as described above, an excellent polyimide material can be provided.

<2. Production method of tt-CHTC>
What is necessary is just to manufacture tt-CHTC which concerns on this invention by isomerizing cis-CHTC, its tetra salt, or its tetraester. The isomerization reaction may be performed, for example, by heating, and the heating temperature may be appropriately controlled according to the raw materials and the like. Details will be described later.

  In addition to the cis-CHTC and cis-CHTC tetra-salts described above, the cis-CHTC tetra-ester may be used as the starting material for the isomerization reaction. In this case, the cis-CHTC tetra-ester used is an isomer mixture. There may be.

  By heating cis-CHTC under controlled temperature conditions to cause an isomerization reaction, two adjacent substituents of cis-CHTC are gradually converted into a trans isomer structure with small steric hindrance. In the present specification, the “isomer mixture” means a mixture of stereoisomers of a cis-cis-cis isomer and a partially containing trans structure.

  As cis-CHTC etc. to be subjected to the isomerization reaction, commercially available products, salts thereof, or esterified products thereof can be used, and those synthesized by a conventionally known method may be used. As a synthesis method of cis-CHTC, for example, pyromellitic acid may be hydroreduced with a rhodium catalyst, or pyromellitic acid tetraester may be hydroreduced and hydrolyzed. Regardless of which raw material is used, the same isomerization reaction behavior is exhibited by heating under controlled temperature conditions. Therefore, the obtained tt-CHTC can be similarly treated in the dehydration cyclization (anhydration) reaction described later.

  In the isomerization reaction, cis-CHTC or the like is dissolved in a solvent and heated. Although it does not specifically limit as this solvent, What is necessary is just to use the organic solvent etc. which are inactive with respect to water, a catalyst, and a raw material. When cis-CHTC or a tetra salt thereof is used as a raw material, it is preferable to use water as a solvent. This is because cis-CHTC or a tetra salt thereof has higher solubility in hot water than solubility in an organic solvent. Moreover, when using cis-CHTC tetraester as a raw material, it is preferable to use an organic solvent. This is because the tetraester has a higher solubility in organic solvents than in water.

  Hereinafter, as specific examples of the production method of tt-CHTC, a case where cis-CHTC is used as a raw material, a case where a tetra salt of cis-CHTC is used, and a case where a tetra ester of cis-CHTC is used will be described.

[2-A. Isomerization reaction of cis-CHTC]
First, the isomerization reaction when cis-CHTC is used as a raw material will be described. The isomerization reaction is preferably carried out in water because of its high solubility in water, especially hot water, but is not limited thereto.

  Moreover, it is good to heat in the case of isomerization reaction. Although it does not specifically limit as temperature of a heating, It is preferable that it is high temperature, specifically 180-300 degreeC is preferable and 200-260 degreeC is more preferable. If it is the range of 180-300 degreeC, a favorable reaction rate can be obtained and two adjacent substituents can be easily converted into a trans body structure. Also, within this temperature range, no special pressure resistance performance is required, and various conventionally known heating devices and the like can be used as the reaction device, so that the isomerization reaction can be performed more easily.

  In the isomerization reaction using cis-CHTC as a raw material, cis-CHTC itself functions as an acid catalyst. Therefore, the form using cis-CHTC as a raw material is advantageous in that it can be carried out without a catalyst.

  In addition, you may use a catalyst separately. In the case of using a catalyst separately, the catalyst may be added to a solvent in which cis-CHTC is dissolved. It is more preferable to carry out the isomerization reaction in a state where both cis-CHTC and the catalyst are dissolved in a solvent.

  The amount of water used in the reaction is not particularly limited, and may be set according to the presence or absence of a catalyst and the type of catalyst. For example, 100 to 800 parts by weight of water may be added to cis-CHTC.

  In addition, the reaction time of the isomerization reaction is not particularly limited, and may be set as appropriate according to the presence or absence of a catalyst, the type of catalyst, the reaction temperature, and the like. For example, the isomerization reaction can be sufficiently performed for 3 to 10 hours.

  In addition, when using the above-mentioned separate catalyst, the specific example of the catalyst is not particularly limited, but an acid stronger than cis-CHTC is preferable, and hydrochloric acid, sulfuric acid are preferably used as the acid catalyst. And inorganic acids such as nitric acid, phosphoric acid and hydrofluoric acid; organic acids such as oxalic acid and d-tartaric acid, p-toluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid; and the like. Of these, water-soluble ones that are easy to remove are preferable, and nitric acid and the like that have high acid strength and hardly leave acid traces are particularly preferable. In addition, it is necessary to select an acid catalyst according to the performance (acid tolerance etc.) of the apparatus to be used. Moreover, even when any acid catalyst is used, the amount used is not limited, and is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight with respect to cis-CHTC. Used in. In addition, there exists an advantage that reaction advances rapidly, so that the usage-amount of a catalyst is large. On the other hand, if the amount of catalyst used is excessive, the amount of cis-CHTC treated may be reduced.

  In addition, the reaction solution after the isomerization reaction may be cooled. Although the temperature of cooling is not specifically limited, 0-40 degreeC is preferable, More preferably, it is 0-20 degreeC. Moreover, what precipitated by cooling may be collect | recovered by filtration etc. and you may dry. In addition, you may cool, after concentrating the said reaction liquid as needed.

[2-B. Isomerization reaction of tetra salt of cis-CHTC]
Next, an isomerization reaction in the case of using a cis-CHTC tetra salt as a raw material will be described. In this case, it is good to isomerize by heating at least one tetra salt among cis-CHTC and an isomer mixture containing the cis-CHTC.

  Moreover, it is preferable to carry out an isomerization reaction in a good solvent for the alkali and CHTC tetra salt described below, particularly in water. The amount of water used in the reaction is not particularly limited, but at least the minimum amount for dissolving the neutralized salt described later is necessary. When using sodium hydroxide specifically, 200-800 weight part water is added with respect to cis-CHTC.

  The tetra salt of cis-CHTC may be prepared by adding cis-CHTC to an alkali (for example, an alkali solution). At this time, it is preferable to stir for about 30 minutes. Examples of usable alkali include alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate; alkaline earth metals such as magnesium hydroxide and calcium hydroxide; Etc. Among these, sodium hydroxide and potassium hydroxide are particularly preferable from the viewpoints of low cost and availability and stability of the formed salt. Moreover, when using any alkali, as the usage-amount, 4-6 equivalent is preferable with respect to cis-CHTC, and 4-5 equivalent is especially preferable. If 4 equivalents or more are added, not only will the reaction proceed quickly, but the solubility of cis-CHTC will increase due to the formation of alkali salts, and the risk of corrosion of the metal reaction vessel will be reduced. be able to. On the other hand, if the amount of alkali used is excessive, the amount of cis-CHTC treated may be reduced, but if it is 6 equivalents or less, there is no such fear and the production efficiency is improved. Further, a cis-CHTC tetra-salt can be synthesized by subjecting the salt obtained by reacting the above alkali and pyromellitic acid to hydrogen reduction according to a known method, and can be directly subjected to an isomerization reaction.

  The isomerization reaction conditions other than those described here can be carried out in the same manner as the cis-CHTC isomerization reaction described above, but can be carried out even at lower temperatures because the reaction is accelerated by the influence of alkali. The specific temperature is preferably in the range of 130 to 250 ° C. because a better reaction rate can be obtained and the cis-CHTC salt can be easily converted into the tt-CHTC salt.

  You may obtain tt-CHTC by neutralizing the tetra salt of tetracarboxylic acid by adding a strong acid after an isomerization reaction. The type of strong acid used for neutralization is not particularly limited, but those with strong acid strength are preferred, and neutralization proceeds efficiently with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrofluoric acid. More preferable. Of these, hydrochloric acid is particularly preferred because it is inexpensive and hardly leaves acid traces. Moreover, although the usage-amount of the strong acid for neutralizing an alkali is not specifically limited, What is necessary is just to use 1-1.2 equivalent with respect to the said alkali. This amount can sufficiently prevent the tt-CHTC salt from remaining.

  Neutralization reduces the solubility of tt-CHTC in water, and tt-CHTC can be efficiently precipitated and recovered by filtration or the like. By drying this, tt-CHTC having high purity can be obtained. . At this time, the salt generated by neutralization is dissolved in water and can be easily removed. Moreover, you may concentrate the aqueous solution containing tt-CHTC as needed. Further, in order to lower the metal content such as sodium, crystallization with water may be performed again.

[2-C. Isomerization reaction of tetraester of cis-CHTC]
Next, an isomerization reaction using cis-CHTC tetraester as a raw material will be described. In this case, it is good to carry out an isomerization reaction by heating at least one tetraester among cis-CHTC and an isomer mixture containing the same. Since the ester is generally poorly soluble in water, an organic solvent is preferable as the solvent.

  As the tetraester of cis-CHTC, for example, those that are easily synthesized or available, such as tetramethyl ester and tetraethyl ester, may be used. For example, a commercially available tetraesterified product of cis-CHTC may be used, or one synthesized by a known method may be used. The method for synthesizing the cis-CHTC tetraester is not particularly limited. For example, pyromellitic acid tetraethyl ester may be hydroreduced with a nickel catalyst, or cis-CHTC may be reacted with an alcohol to be esterified. Also good.

  Further, specific examples of the organic solvent are preferably solvents that do not react with alkali, and specifically, alcohols such as methanol and ethanol; ethers such as ethyl ether and tetrahydrofuran; and the like can be preferably used. The amount of the organic solvent is not particularly limited, but 200 to 1000 parts by weight can be added to 100 parts by weight of cis-CHTC tetraester.

  In addition, when a cis-CHTC tetraester is used as a raw material, it is preferable to carry out at a relatively low temperature by adding a catalyst in consideration of thermal stability. As the catalyst, a basic catalyst is preferable because it has a large reaction promoting effect, and among them, a catalyst that is soluble in an organic solvent is preferable. For example, alkali metal alkoxides such as lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide and sodium ethoxide, or organic bases such as diazabicyclononene (DBN) and diazabicycloundecene (DBU) are suitable. Used for. Even when any basic catalyst is used, it is not particularly limited as long as the catalyst is a combination in which the catalyst is dissolved in a solvent and is inert to each other, and a plurality of types can be used in combination.

  Moreover, as temperature heated in the case of an isomerization reaction, 40-120 degreeC is preferable and 50-800 degreeC is more preferable. If it is the range of 40-120 degreeC, a favorable reaction rate can be obtained and a cis-isomer can be easily converted into a trans-isomer.

  As described above, the isomerization reaction of the cis-CHTC tetraester is preferably performed at a relatively low temperature. For example, cis-CHTC tetramethyl ester is added to 1 to 20% by weight of sodium methoxide and refluxed in methanol, so that conversion to a trans form proceeds. At this time, since the esterified product of isomerized cis-CHTC has a reduced solubility in alcohol and precipitates, it can be recovered by filtration or the like.

  After the isomerization reaction, the cis-CHTC tetraester can be hydrolyzed by known methods. For example, it can be obtained as tt-CHTC by hydrolysis in the presence of an acid catalyst or a basic catalyst.

<3. Production method of tt-CHTCA>
The method for producing tt-CHTCA according to the present invention may include a step of dehydration reaction by heating in the presence of a dehydrating agent. Thereby, tt-CHTCA according to the present invention having high reactivity (polymerizability) can be obtained.

  As tt-CHTC to be subjected to the dehydration reaction, tt-CHTC obtained by the above isomerization reaction may be used. In addition, when a catalyst is used in the isomerization reaction and / or hydrolysis as described above, impurities derived from the catalyst may be mixed into the obtained tt-CHTC. Therefore, it is preferable to subject the obtained tt-CHTC to a dehydration reaction after purification by a known method such as recrystallization.

  The dehydrating agent is not particularly limited as long as the dehydrating agent comes into contact with tt-CHTC. For example, tt-CHTC and the dehydrating agent may be mixed in a solvent. As the dehydrating agent, lower organic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride are preferable, and among them, acetic anhydride which is advantageous after removal and economical advantage is particularly preferable. Although the usage-amount of a dehydrating agent is not specifically limited, 2-50 equivalent is preferable with respect to tt-CHTC, Most preferably, it is 4-20 equivalent. If it is 2 to 50 equivalents, tt-CHTCA can be precipitated in a high yield without being sufficiently dehydrated and without increasing the amount of tt-CHTCA dissolved. Note that it is not always necessary to completely dissolve tt-CHTC for the dehydration reaction, and the dehydration reaction may be performed in a heterogeneous system.

  About heating temperature, it is good to carry out in the range of 40-160 degreeC. The reaction rate increases as the reaction temperature increases. However, tt-CHTCA has a large distortion and an unstable structure. If the temperature is too high, the steric structure may be converted from a trans form to a cis form. Therefore, it is not preferable. Therefore, the temperature range of the dehydration reaction is more preferably 50 to 120 ° C. The dehydration reaction time may be appropriately set according to conditions such as the type of dehydrating agent to be used, reaction temperature, etc., but is preferably 0.5 to 20 hours. The dehydration reaction can be sufficiently performed in this time.

  By the above dehydration reaction, a suspension suspended in the dehydrating agent used by tt-CHTCA can be obtained. After the dehydration reaction, a powder of tt-CHTCA can be recovered by filtering the obtained suspension. Moreover, you may concentrate the said suspension as needed. Furthermore, by removing the dehydrating agent by drying under reduced pressure or the like, the dehydrating agent can be suitably used for the polymerization step of the polyimide precursor (polyamic acid) described later.

  In addition, the manufacturing method of tetracarboxylic dianhydride characterized by including the process of carrying out the dehydration reaction by heating (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid in presence of a dehydrating agent, and this The tetracarboxylic dianhydride obtained by the above is also included in the scope of the present invention.

<4. Polyimide precursor according to the present invention>
The polyimide precursor according to the present invention has the general formula (1)

(In the above general formula (1), X represents a tetravalent cyclohexane group, and R represents a hydrogen atom, a trialkylsilyl group, or a linear, branched or cyclic alkyl group or alkoxyl group having 1 to 12 carbon atoms. A represents a divalent aromatic group or aliphatic group, and the configuration of X is represented by the following formula (2):

The bonding position between the X and the two amide groups and two carboxyl groups bonded to the X is represented by either the following formula (3) or (4).

(In formulas (3) and (4), Y represents two amide groups bonded to X and Z represents two carboxyl groups bonded to X))) Is the body.

  A highly transparent and low dielectric constant polyimide can be obtained by ring-closing (imidizing) the polyimide precursor according to the present invention. That is, the polyimide precursor according to the present invention is excellent as a raw material for polyimide.

  Although an example of the manufacturing method of a polyimide precursor is demonstrated below, it is not limited to this.

  The polyimide precursor according to the present invention may be produced by polymerizing the tt-CHTCA according to the present invention and a diamine. Hereinafter, the process of polymerizing tt-CHTCA and diamine may be simply referred to as “polymerization process”. In addition, as above-mentioned, it is preferable to make it react with diamine after removing the dehydrating agent used in the manufacturing method of tt-CHTCA based on this invention completely.

  More specifically, in the polymerization step, tt-CHTCA powder may be added to the diamine solution and stirred at room temperature. The stirring time is not particularly limited, and may be performed until the tt-CHTCA powder is sufficiently dissolved. Thus, the polyimide precursor which concerns on this invention can be easily manufactured by using tt-CHTCA and diamine which concern on this invention as a raw material. Although it does not specifically limit as the usage-amount of diamine, It is preferable from a viewpoint of raising a polymerization degree that it is a substantially equimolar amount with respect to tt-CHTCA.

  In order to prepare the diamine solution, as a solvent for dissolving diamine, a monomer (tt-CHTCA and diamine according to the present invention) and a produced polyamic acid (polyimide precursor according to the present invention) are dissolved. The solvent is not particularly limited as long as it is a solvent that does not react with these monomers. For example, aprotic solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like can be particularly preferably used.

  In the polymerization step, by using a dialkyl ester dichloride of tt-CHTC instead of tt-CHTCA in the presence of a deoxidizing agent such as pyridine, an alkyl ester of polyamic acid (in the general formula (1), R is A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or a linear, branched or cyclic alkoxyl group having 1 to 12 carbon atoms).

  In the polymerization step, the diamine is converted into a ditrialkylsilylated product in advance, and tt-CHTCA is added thereto to thereby add a trialkylsilyl ester of polyamic acid (in the general formula (1), R is trivalent). An alkylsilyl group). Although it does not specifically limit as a trialkyl silylating agent which can be used in the case of trialkyl silylation of diamine, N, O-bis (trimethyl silyl) trifluoroacetamide, N, O- in addition to halogenated alkyl silanes, such as a trimethyl silyl chloride. Examples include bis (trimethylsilyl) acetamide and the like.

  Moreover, it does not specifically limit as diamine used in order to manufacture the polyimide precursor which concerns on this invention, What is necessary is just to select suitably according to the use etc. of the polyimide precursor to manufacture. For example, aromatic diamine, aliphatic diamine, etc. are mentioned. Or they can be used in combination.

  Specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4. '-Methylenedianiline, 4,4'-methylenebis (3-methylaniline), 4,4'-methylenebis (3-ethylaniline), 4,4'-methylenebis (2-methylaniline), 4,4'- Methylenebis (2-ethylaniline), 4,4′-methylenebis (3,5-dimethylaniline), 4,4′-methylenebis (3,5-diethylaniline), 4,4′-methylenebis (2,6-dimethyl) Aniline), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiph Nyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 2,2′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diamino Benzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, o-tolidine, m-tolidine, 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, bis (4- (3-a Nophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, p-terphenylenediamine, 2,2′- Bis (trifluoromethyl) benzidine, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diaminodiphenyl ether 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 2,2′-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4- Bis (3-aminophenoxy) benzene, 1,3-bis (4-amino) Phenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- ( 4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylenedianiline, 4,4'-methylenebis (3-methylaniline) ), 4,4′-methylenebis (3-ethylaniline), 4,4′-methylenebis (2-methylaniline) 4,4′-methylenebis (2-ethylaniline), 4,4′-methylenebis (3,5-dimethylaniline), 4,4′-methylenebis (3,5-diethylaniline), 4,4′-methylenebis (2,6-dimethylaniline), 4,4′-methylenebis (2,6-diethylaniline) and the like can be exemplified. These may be used alone or in combination of two or more.

  Specific examples of the aliphatic diamine include 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (3-methylcyclohexylamine), 4,4′-methylenebis (3-ethylcyclohexylamine), 4, 4'-methylenebis (3,5-dimethylcyclohexylamine), 4,4'-methylenebis (3,5-diethylcyclohexylamine), isophoronediamine, trans-1,4-cyclohexanediamine, cis-1,4-cyclohexanediamine 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diamy Adamantane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-penta Methylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine) and the like. These may be used alone or in combination of two or more.

  In addition to tt-CHTCA according to the present invention, tetracarboxylic dianhydrides other than tt-CHTCA such as aromatic tetracarboxylic dianhydride components and aliphatic tetracarboxylic dianhydrides may be used. Such a tetracarboxylic dianhydride may be selected within a range that does not significantly impair the polymerization reactivity of the polyamide precursor and the required characteristics of the polyimide, and is not limited as long as it can be polymerized with the diamine. The copolymerizable aromatic tetracarboxylic dianhydride is not particularly limited, but pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropanoic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propanoic dianhydride, hydroquinone bis (trimellitate) Anhydride), 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more as copolymerization components.

  The aliphatic tetracarboxylic dianhydride that can be partially used is not particularly limited as long as it does not significantly impair the polymerization reactivity and the required characteristics of the polyimide when producing the polyimide precursor according to the present invention. 2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride Bicyclo [2.2.2] heptanetetracarboxylic dianhydride, 5- (dioxotetrahydrofuryl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5- Dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo-3,3 ', 4,4' Tetracarboxylic dianhydride, 3c-carboxymethylcyclopentane-1r, 2c, 4c-tricarboxylic acid 1,4: 2,3-dianhydride, cis, cis, cis, cis-1,2,4,5- Examples include cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc. More than one type can be used in combination.

  Conventionally, it has been clear that polyimides having a CHTCA block (CHTCA structure) have excellent characteristics such as high transparency and low dielectric constant, but cis, cis, cis-1,2, Since 4,5-cyclohexanetetracarboxylic dianhydride has low reactivity with diamine, it was difficult to produce a polyimide precursor (polyamic acid) having a high degree of polymerization. However, when the raw material for synthesis of the polyimide precursor is used, the tetracarboxylic dianhydride produced by the production method of the present invention is contained in CHTCA at 20% by weight, preferably 50% by weight or more. A polyimide precursor can be produced, and a polyimide having a CHTCA block that has been known and maintains excellent characteristics can be easily obtained at a high degree of polymerization.

  The solvent used in the polymerization reaction is preferably an aprotic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. If the polyimide precursor to be dissolved does not react with the monomer, there is no problem and there is no particular limitation. Specifically, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε -Cyclic ester solvents such as caprolactone, α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4- Phenol solvents such as chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably used. Furthermore, other common organic solvents, such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, ptyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirit, petroleum naphtha solvent Etc. can also be added and used.

  The polyimide precursor according to the present invention can be isolated as a powder by dropping, filtering and drying the polymerization solution in a poor solvent such as water or methanol. The amount of the solvent is not limited as long as dripping or the like can be performed sufficiently.

  The higher the intrinsic viscosity of the polyimide precursor according to the present invention, the better. However, it is preferably at least 0.5 dL / g or more, more preferably 1.0 dL / g or more. When it is less than 0.5 dL / g, the film forming property is remarkably deteriorated, and a serious problem such as cracking of the cast film may occur.

  A polymer dissolution accelerator, that is, a metal salt such as lithium bromide or lithium chloride, which is often added during polymerization of polyamide or the like may not be used at all for the polyimide precursor polymerization reaction in the present invention. When these metal salts remain in the polyimide film even if there is a trace amount of metal ions, the reliability as an electronic device is remarkably lowered. The polyimide precursor according to the present invention is extremely useful because it is not necessary to use such metal salts.

<5. Polyimide according to the present invention>
The polyimide according to the present invention has the general formula (5)

(In formula (5), X represents a tetravalent cyclohexane group, A represents a divalent aromatic group or aliphatic group, and the configuration of X is represented by the following formula (2).)

It is a polyimide which has a repeating unit represented by these.

  The polyimide according to the present invention can be produced, for example, by subjecting the polyimide precursor obtained by the above method to a dehydration ring-closing reaction (imidation reaction). At this time, examples of the usable form of polyimide include a film, a metal substrate / polyimide film laminate, a powder, a molded body, and a solution.

  As an example, a method for producing a polyimide film according to the present invention will be described. A polyimide precursor polymerization solution (varnish) is cast on a substrate of glass, copper, aluminum, stainless steel, silicon or the like and dried using an oven or the like. The drying temperature is preferably 40 to 180 ° C, more preferably 50 to 150 ° C. The polyimide film according to the present invention can be produced by heating the obtained polyimide precursor film in a vacuum, in an inert gas such as nitrogen, or in the air. The heating temperature is preferably 200 ° C. or higher from the viewpoint of sufficiently carrying out the imidization ring-closing reaction, and 400 ° C. or lower from the viewpoint of the thermal stability of the produced polyimide film. More preferably, it is 250-350 degreeC. The imidation is desirably performed in a vacuum or in an inert gas, but may be performed in air if the imidization temperature is not too high.

  Also, the imidization reaction can be performed by immersing the polyimide precursor film in a solution containing a dehydrating cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine instead of heat treatment. is there. In addition, a polyimide precursor film partially or completely imidized is prepared by previously charging and stirring these dehydrating cyclization reagents in a polyimide precursor varnish, and casting and drying them on the substrate. You can also. This may be further heat-treated in the above temperature range.

  In addition, when the polyimide itself to be produced is dissolved in the solvent used in the imidization reaction, the polyimide precursor polymerization solution is directly or diluted with the same solvent, and then heated to 150 to 200 ° C., according to the present invention. A polyimide solution (varnish) can be easily produced. When insoluble in a solvent, crystalline polyimide powder may be obtained as a precipitate. At this time, an organic solvent such as toluene or xylene may be added to azeotropically distill off water or the like, which is a by-product of the imidization reaction. Further, a base such as γ-picoline can be added as a catalyst. After imidation, this reaction solution can be dropped and filtered in a large amount of poor solvent such as water or methanol to isolate the polyimide as a powder. Alternatively, the polyimide powder can be redissolved in the polymerization solvent to obtain a polyimide varnish.

  The polyimide according to the present invention can be polymerized in one step without isolating the polyimide precursor by reacting the diamine and tt-CHTCA according to the present invention at a high temperature in a solvent. At this time, the reaction solution may be maintained in a range of 130 to 250 ° C., preferably 150 to 200 ° C., from the viewpoint of promoting the reaction. Moreover, when a polyimide is insoluble in the solvent used for imidation reaction, a polyimide is obtained as a precipitate, and when soluble, it is obtained as a varnish of polyimide. The polymerization solvent is not particularly limited. Examples of usable solvents include aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), and dimethyl sulfoxide. More preferably, a phenol solvent such as m-cresol or an amide solvent such as NMP is used. In order to azeotropically distill off water, which is a by-product of the imidization reaction, to these solvents, an organic solvent such as toluene or xylene can be added. A base such as γ-picoline can be added as an imidization catalyst. After the reaction, the solution can be dropped and filtered into a large amount of poor solvent such as water or methanol to isolate the polyimide as a powder. When the polyimide is soluble in a solvent, the powder can be redissolved in the above solvent to obtain a polyimide varnish.

  You may form an alicyclic polyimide film by apply | coating the said polyimide varnish on a board | substrate, and making it dry. Although the temperature of drying is not specifically limited, For example, it is 40-400 degreeC, Preferably it is 100-350 degreeC.

  Moreover, you may produce the molded object of a polyimide by heat-compressing the obtained polyimide powder. Although it does not specifically limit as temperature at the time of heat compression, For example, it is 200-450 degreeC, Preferably it is 250-430 degreeC.

  It is an isomer of polyimide by adding and stirring a dehydrating reagent such as N, N-dicyclohexylcarbodiimide or trifluoroacetic anhydride in the polyimide precursor solution and reacting at 0 to 100 ° C., preferably 0 to 60 ° C. Polyisoimide is formed. The isoimidization reaction can also be performed by immersing the polyimide precursor film in a solution containing the dehydrating reagent. After polyisoimide varnish is formed in the same procedure as above, it can be easily converted to polyimide by heat treatment at 250 to 450 ° C., preferably 270 to 400 ° C.

  The polyimide precursor according to the present invention and the polyimide according to the present invention include an oxidation stabilizer, a filler, an adhesion promoter, a silane coupling agent, a photosensitizer, a photopolymerization initiator, a sensitizer, and end-capping as necessary. You may add additives, such as an agent and a crosslinking agent.

<6. Utilization of polyimide precursor and polyimide according to the present invention>
[Photosensitive resin composition according to the present invention]
The photosensitive resin composition according to the present invention (hereinafter sometimes referred to as “photosensitive polyimide precursor”) contains the polyimide precursor according to the present invention and a photosensitive agent. That is, a photosensitive polyimide precursor can also be obtained from the polyimide precursor according to the present invention.

  Although it does not specifically limit as a photosensitive agent, The diazo naphthoquinone type photosensitive agent mentioned later is preferable. In addition, although it does not specifically limit as a quantity of a photosensitizer, 10 to 40 weight% is preferable with respect to a polyimide precursor, and it is more preferable that it is 15 to 30 weight%.

  In the photosensitive resin composition according to the present invention, the polyimide precursor and the photosensitive agent according to the present invention may be dissolved in a solvent. The solvent is not limited as long as the polyimide precursor and the photosensitizer can be dissolved, and various organic solvents may be used.

  Next, an example of a method for obtaining the photosensitive resin composition according to the present invention will be described. First, a diazonaphthoquinone photosensitizer is added and dissolved in an organic solvent solution in which the polyimide precursor according to the present invention is dissolved. Thereby, the photosensitive resin composition can be obtained.

  Next, a structure provided with a pattern obtained using the photosensitive resin composition according to the present invention will be described. That is, the structure in which the photosensitive resin composition according to the present invention is subjected to pattern exposure on a substrate, developed after pattern exposure, and heat-cured after development is also formed on the structure. This is within the scope of the present invention. In addition, when using polyimide as a buffer coat film in a semiconductor element, it is necessary to make a hole for connecting to an external circuit. Depending on the use of the semiconductor element, a through hole or via hole of about 3 to 20 μm is required. Perform drilling. Polyimide derived from the photosensitive resin composition according to the present invention is suitable as a material for forming such a buffer coat film.

  First, the photosensitive resin composition according to the present invention is subjected to pattern exposure. In pattern exposure, a photosensitive resin composition may be applied on a substrate and exposed to ultraviolet rays through a photomask having a target pattern.

  For example, a spin coater or a bar coater is used to apply on a substrate such as copper, silicon, or glass. Next, a film of a photosensitive polyimide precursor having a film thickness of 1 to 10 μm, for example, can be obtained by drying with warm air at 40 to 120 ° C. for 0.1 to 3 hours under light shielding. The temperature and time for hot air drying can be changed as appropriate.

  The polyimide precursor according to the present invention is originally soluble in alkali when R in the general formula (1) is a hydrogen atom, but is formed in a state where a diazonaphthoquinone photosensitizer is dispersed. Since the diazonaphthoquinone (DNQ) photosensitizer acts as a dissolution inhibitor, the obtained film itself becomes alkali-insoluble. On the other hand, when this film is irradiated with ultraviolet rays through a photomask, the diazonaphthoquinone photosensitizer in the exposed portion is changed to alkali-soluble indenecarboxylic acid by a photoreaction, so that only the exposed portion is soluble in the aqueous alkali solution. Therefore, a positive pattern can be formed. In addition, even if DNQ is added, if the alkali solubility is too high and pattern formation is difficult, it is clearer by partially controlling the alkali solubility by alkyl esterification, alkoxy esterification, or trimethylsilylation. A positive pattern can be formed.

  Specific examples of the diazonaphthoquinone photosensitizer include 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-2-diazide-4-sulfonic acid low molecular hydroxy compounds such as 2,3 , 4-trihydroxybenzophenone, 1,3,5-trihydroxybenzene, 2- and 4-methyl-phenol, esters of 4,4′-hydroxy-propane, and the like, but are not limited thereto.

  When the blending ratio of the diazonaphthoquinone photosensitizer in this positive photosensitive resin composition is too small, the difference in solubility between the exposed and unexposed areas is too small, and pattern formation cannot be achieved by development, and there are too many In addition to the possibility of adversely affecting the film physical properties (toughness, glass transition temperature, etc.) of polyimide, there is a risk that the film loss after imidization will be large. It is 10 to 40%, more preferably 15 to 30%.

  The step of obtaining the photosensitive polyimide precursor film is preferably performed at 120 ° C. or lower. Above this temperature, the diazonaphthoquinone photosensitizer may start to thermally decompose. When the film is formed at 60 ° C., a large amount of solvent remains in the coating film. In that case, prebaking may be performed at 80 to 120 ° C. for 1 to 30 minutes prior to the exposure operation, but it is also effective to immerse the coating film in water for 1 to 5 minutes. The residual solvent may cause swelling of the film and / or pattern collapse during development, and it is preferable to sufficiently remove the residual solvent in order to obtain a clear pattern.

  The photosensitive resin composition film is irradiated with i-line of a high-pressure mercury lamp at room temperature for 10 seconds to 1 hour through a photomask, and 0.05 to 10% by weight, preferably 0.1 to 5% by weight of tetramethylammonium. By developing with an aqueous hydroxide solution at room temperature for 10 seconds to 10 minutes and further rinsing with pure water, a clear positive pattern can be obtained.

  The development may be performed by a conventionally known method. For example, an alkaline aqueous solution may be used, but is not limited thereto. When developing with an aqueous alkali solution, if the difference in solubility between the exposed and unexposed areas is insufficient, a clear relief pattern may be difficult to obtain. In this case, it is possible to control the solubility in an alkaline aqueous solution by synthesizing a copolymer mainly composed of the polyimide precursor according to the present invention using an appropriate monomer. Although it does not specifically limit as a copolymerization component which can be used in this case, The monomer containing a fluorine group is used suitably.

  By heating and curing a fine pattern of a polyimide precursor formed on a substrate in air, in an inert gas atmosphere such as nitrogen or in vacuum, at a temperature of 200 ° C. to 430 ° C., preferably 250 ° C. to 400 ° C. A clear polyimide film pattern is obtained. In this case, imidization can also be performed chemically using a dehydrating cyclization reagent. That is, the pattern of the polyimide film can also be obtained by a method of immersing the polyimide precursor film formed on the substrate in acetic anhydride containing a basic catalyst such as pyridine and triethylamine at room temperature for 1 minute to several hours. . The photosensitive resin composition according to the present invention, which contains a DNQ-based agent as a photosensitive agent, particularly has a fine pattern forming ability, high i-line transmittance, heat resistance, and electrical insulation. It can be suitably used as a material.

[Display Substrate According to the Present Invention]
The display substrate according to the present invention only needs to contain the polyimide according to the present invention. Since the display substrate according to the present invention is excellent in transparency and flexibility, it can be applied to various displays such as a liquid crystal display and an organic electroluminescence display. These may be flexible displays. That is, the display substrate according to the present invention can include, for example, a liquid crystal display substrate, an organic electroluminescence display substrate, and a flexible display substrate in which these are configured flexibly.

  As a characteristic required for applying the polyimide according to the present invention to a plastic substrate for a flexible liquid crystal display, the glass transition temperature of the polyimide is preferably 230 ° C. or higher, and more preferably 250 ° C. or higher. The light transmittance at a wavelength of 400 nm, which is an index of transparency, is preferably 60% or more, more preferably 70% or more, and still more preferably 80%. In addition, the polyimide film can be applied to the industrial field as long as it is not broken by a 180 ° bending test as an index of film toughness. However, the elongation at break in the tensile test is preferably 10% or more, more preferably 20% or more, and still more preferably. Is 30% or more. If the birefringence is 0.01 or less, there is no serious problem in applying to an optical material such as the above-mentioned display, but it is more preferably 0.005 or less.

[Interlayer Insulating Film of Integrated Circuit According to the Present Invention]
The interlayer insulating film of the integrated circuit according to the present invention only needs to contain the polyimide according to the present invention.

  As a characteristic required for applying the polyimide according to the present invention to an interlayer insulating film of an integrated circuit, the glass transition temperature of the polyimide is preferably 250 ° C. or higher, and more preferably 300 ° C. or higher. In addition, the polyimide film is sufficiently applicable to various industrial fields using an integrated circuit unless it is broken by a 180 ° bending test as an index of film toughness. The dielectric constant is preferably 2.8 or less, and more preferably 2.7 or less. The polyimide according to the present invention can also be used as a buffer coat for integrated circuits.

[Liquid crystal alignment film according to the present invention]
The liquid crystal alignment film according to the present invention only needs to contain polyimide. That is, the polyimide precursor according to the present invention or the polyimide according to the present invention can be applied to a liquid crystal alignment film material. The polyimide according to the present invention can improve solubility in organic solvents by using a diamine component containing a fluorine group, a sulfone group, etc., and by applying, drying and rubbing a polyimide varnish, liquid crystal alignment It can be a membrane.

  Since the polyimide according to the present invention has an alicyclic structure, the glass transition temperature is 250 ° C. or higher, and the short-term heat resistance required for the production of TFT type liquid crystal displays and semiconductor chips is sufficiently high. There is no problem in industrial applications.

  Moreover, the tt-CHTCA according to the present invention can be used as a copolymerization component for the purpose of increasing the molecular weight without greatly sacrificing the physical properties of various polyimides used in various industrial fields.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to these Examples. In addition, the physical-property value in the following examples and comparative examples was measured with the following method.

<Infrared absorption spectrum>
Using a Fourier transform infrared spectrophotometer (FTIR-8400S manufactured by Shimadzu Corporation, FT-IR5300 or FT-IR350 manufactured by JASCO Corporation), red of the tt-CHTCA, polyimide precursor and polyimide thin film according to the present invention by the transmission method The external absorption spectrum was measured. Moreover, in order to confirm the molecular structure of tt-CHTC and tt-CHTCA according to the present invention, an infrared absorption spectrum was measured by the KBr method.

<Differential scanning calorimetry (melting point and melting curve)>
The melting points and melting curves of tt-CHTC and tt-CHTCA according to the present invention were measured using a differential scanning calorimeter (DSC3100) manufactured by Bruker Ax in a nitrogen atmosphere at a heating rate of 2 ° C./min.

<Single crystal X-ray structural analysis>
For single crystal X-ray structure analysis, measurement was performed at a measurement temperature of 294 K, an X-ray source CuKα ray, a tube voltage of 50 kV, and a tube current of 30 mA using a single crystal X-ray structure analyzer (SMART APEXII) manufactured by Bruker Japan.

<Powder X-ray diffraction pattern>
For the powder X-ray diffraction pattern, a powder X-ray diffractometer (M03XHF22) manufactured by Bruker AXS Co., Ltd. was used, measurement temperature 294K, X-ray source CuKα ray, tube voltage 45 kV, tube current 40 mA, sampling step 0.02 °, Measurement was performed at a scanning speed of 4 ° / min and a measurement range 2θ = 5 to 60 °.

<Intrinsic viscosity>
A 0.5 wt% polyimide precursor solution (solvent: N, N-dimethylacetamide or NMP) was measured at 30 ° C. using an Ostwald viscometer.

<Glass transition temperature: Tg>
The glass transition temperature of the polyimide film was determined from the loss peak at a frequency of 0.1 Hz and a heating rate of 5 ° C./minute by dynamic viscoelasticity measurement using a thermomechanical analyzer (TMA4000) manufactured by Bruker AXS.

<Linear thermal expansion coefficient: CTE>
By using a thermomechanical analyzer (TMA4000) manufactured by Bruker AXS Co., Ltd., the elongation of the test piece at a load of 0.5 g / film thickness of 1 μm and a heating rate of 5 ° C./min is 100 to 200 ° C. The linear thermal expansion coefficient of the polyimide film was determined as an average value in the range.

<5% weight loss temperature: Td ⁵ >
When the initial weight of the polyimide film is reduced by 5% in the temperature rising process at a heating rate of 10 ° C./min in nitrogen or air using a thermogravimetric analyzer (TG-DTA2000) manufactured by Bruker AXS The temperature of was measured. Higher values indicate higher thermal stability.

<Cutoff wavelength (transparency)>
Using a UV-visible spectrophotometer (V-530) manufactured by JASCO Corporation, the visible / ultraviolet transmittance from 200 nm to 900 nm was measured. The wavelength (cutoff wavelength) at which the transmittance was 0.5% or less was used as an index of transparency. The shorter the cutoff wavelength, the better the transparency of the polyimide film.

<Light transmittance (transparency)>
The light transmittance at 400 nm was measured using an ultraviolet-visible spectrophotometer (V-530) manufactured by JASCO Corporation. The higher the transmittance, the better the transparency of the polyimide film.

<Birefringence>
Using an Abbe refractometer (4T) manufactured by Atago Co., Ltd., the refractive index _{in the} direction parallel to the polyimide film (n _in ) and the direction perpendicular to the polyimide film (n _out ) is measured with an Abbe refractometer (using a sodium lamp, wavelength 589 nm) Birefringence (Δn = n _in −n _out ) was determined from the difference in refractive index.

<Dielectric constant and dielectric loss>
Using an Abbe refractometer (4T) manufactured by Atago Co., based on the average refractive index [nav = (2n _in + n _out ) / 3] of the polyimide film, a polyimide film at 1 MHz according to the following formula: εcal = 1.1 × nav ² The dielectric constant (εcal) of was calculated.

<Elastic modulus, breaking strength, breaking elongation>
Using a tensile tester (Tensilon UTM-2) manufactured by Toyo Baldwin Co., Ltd., a tensile test (stretching speed: 8 mm / min) was performed on a polyimide film test piece (3 mm × 30 mm), and the initial slope of the stress-strain curve From the elongation, the elongation at break (%) was determined from the elongation at the time when the membrane was broken. Higher elongation at break means higher film toughness.

[Example 1]
In this Example 1 and the following Example 2, the following synthesis route (10)

Thus, tt-CHTCA according to the present invention was synthesized. Specifically, it is as follows.

  First, (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic acid was synthesized according to the description in Non-Patent Document 2. 465 g of pyromellitic dianhydride, 175 g of 5% rhodium / carbon catalyst and 2940 g of distilled water were placed in a 5 L volume SUS316 autoclave with a stirrer, and hydrogenated at a reaction temperature of 60 ° C. and a hydrogen pressure of 5 MPa. After 1.5 hours, the reaction solution was taken out and the catalyst was removed by filtration, followed by drying with an evaporator to obtain 449 g of (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic acid (formula 10 (a)). .

  Next, 38 g (0.146 mol) of (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic acid, 24 g (0.600 mol) of sodium hydroxide and 108 g of distilled water were made of SUS316 with a 200 mL capacity stirrer. The mixture was placed in an autoclave and subjected to isomerization reaction at 230 ° C. for 5 hours under a nitrogen atmosphere.

  Next, after cooling the reaction liquid after the isomerization reaction to 30 ° C., the reaction liquid is transferred to a three-necked flask having a volume of 500 mL, and 63 g (0.605 mol) of 35% hydrochloric acid is slowly added dropwise with stirring. As a result, a white precipitate was formed. Further, stirring was continued for 1 hour.

Next, the reaction solution after stirring was subjected to suction filtration to collect a white precipitate, and then dried under reduced pressure at 80 ° C. for 5 hours. As a result, 32.3 g of white powder was obtained. The obtained white powder was heated in 0.5N methanolic hydrochloric acid to be converted into tetramethyl ester and analyzed by gas chromatography. As a result, a peak corresponding to tetramethyl (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylate was obtained. Disappeared completely, and a single peak was detected at different positions. Furthermore, as a result of recrystallizing this white powder from water and performing single crystal X-ray structural analysis, it was confirmed to be tt-CHTC. The three-dimensional structure is shown in FIG. 2 and 3 show NMR spectra. FIG. 1 is a diagram showing the three-dimensional structure of tt-CHTC obtained in this example. FIG. 2 is a diagram showing a ¹ H-NMR spectrum of tt-CHTC obtained in this example, and FIG. 3 is a diagram showing a ¹³ C-NMR spectrum of tt-CHTC obtained in this example.

  The molar yield of the isomerization reaction was 85%.

[Example 2]
A suspension was obtained by mixing 25 g (0.096 mol) of tt-CHTC obtained in Example 1 and 75 g (0.735 mol) of acetic anhydride in a 200-mL flask. The suspension was heated and stirred in an oil bath at 80 ° C. for 7 hours.

  Next, after the suspension after stirring was cooled to 30 ° C., it was filtered and the filtered white powder was dried under reduced pressure at 80 ° C. for 5 hours. As a result, 18.1 g of white powder was obtained.

As a result of measuring the infrared absorption spectrum of the obtained white powder, the O—H stretching vibration near 3000 cm ⁻¹ derived from the carboxyl group disappeared, and absorption bands were observed at 1869 cm ⁻¹ and 1790 cm ⁻¹ . These are absorption bands characteristic of five-membered ring acid anhydrides C = O stretching vibrations, and indicate that five-membered ring acid anhydrides were synthesized by the above reaction. In addition, the white powder has low solubility in organic solvents, low thermal stability, and poor crystallinity, so that a crystal suitable for single crystal X-ray structural analysis could not be obtained. Therefore, 5 g of the white powder, 55 g of distilled water and 0.05 g of 4-dimethylaminopyridine were placed in a 100 mL eggplant type flask and heated at 80 ° C. for 24 hours to synthesize a hydrolyzate (tetracarboxylic acid). The homogeneous aqueous solution thus obtained was cooled to 30 ° C., and the precipitated crystals were collected and subjected to powder X-ray analysis. As a result, this hydrolysis pattern showed the same diffraction pattern as that of the white powder obtained in Example 1. It was confirmed that the stereostructure of the product (tetracarboxylic acid) and the tetracarboxylic acid described in Example 1 were the same. That is, the three-dimensional structure of Example 1 is retained after the dehydration reaction. That is, the white powder obtained by the dehydration reaction is tt-CHTCA. The molar yield of the above dehydration reaction was 84%. Next, the infrared absorption spectrum and NMR spectrum of tt-CHTCA were measured. The results are shown in FIGS. 4 is a diagram showing an infrared absorption spectrum of tt-CHTCA obtained in this example, FIG. 5 is a diagram showing a ¹ H-NMR spectrum, and FIG. 6 is a diagram showing a ¹³ C-NMR spectrum. is there. Moreover, the powder X-ray-diffraction pattern of tt-CHTC obtained in Example 1 and the tetracarboxylic acid obtained by dehydrating and hydrolyzing this was measured, respectively. The results are shown in FIGS. FIG. 7 is a diagram showing a powder X-ray diffraction pattern of tt-CHTC before dehydration, and FIG. 8 is a diagram showing an X-ray diffraction pattern of a hydrolyzate of tt-CHTCA.

Example 3
530 g (13.25 mol) of sodium hydroxide and 2500 g of distilled water were placed in a 5 L SUS316 autoclave equipped with a stirrer and stirred. To the obtained aqueous sodium hydroxide solution, 715 g (3.28 mol) of pyromellitic dianhydride and 28.6 g of 5% ruthenium / carbon catalyst were added, and hydrogenated at a reaction temperature of 160 ° C. and a hydrogen pressure of 8 MPa. Hydrogen absorption stopped after 3 hours. Next, the temperature of the hydrogenation reaction solution was raised to 220 ° C., and the reaction was continued for another 4 hours.

  After removing the catalyst by filtration, the obtained reaction solution was transferred to a three-necked flask with a volume of 10 L, and 1400 g (13.44 mol) of 35% hydrochloric acid was slowly added dropwise with stirring. occured. Further, stirring was continued for 1 hour.

  Next, the reaction solution after stirring was subjected to suction filtration to collect a white precipitate, and then dried under reduced pressure at 80 ° C. for 5 hours. As a result, 676 g of white powder was obtained. The obtained white powder was heated in 0.5N methanolic hydrochloric acid to be converted into tetramethyl ester and analyzed by gas chromatography. As a result, it was confirmed that the obtained white powder was tt-CHTC. The molar yield of the isomerization reaction was 81%. The obtained white powder contained 1991 ppm of sodium.

  Next, 300 g of the obtained tt-CHTC and 1500 g of distilled water were put into a 2 L flask and stirred at 100 ° C. for 2 hours. The obtained homogeneous solution was slowly cooled to 30 ° C. while stirring, and then the precipitated crystals were filtered. The obtained crystals were dried under reduced pressure at 80 ° C. for 5 hours. As a result, 227.7 g of white crystals were obtained. The yield of the above recrystallization was 76%, and the sodium content was 5 ppm.

  200 g (0.77 mol) of the obtained dianhydride crystals and 800 g (7.84 mol) of acetic anhydride were placed in a 2 L flask, heated and stirred in an oil bath at 80 ° C. for 7 hours. The obtained suspension was cooled to 30 ° C., filtered, and the filtered white powder was dried under reduced pressure at 80 ° C. for 5 hours. As a result, 148.2 g of tt-CHTCA was obtained. The molar yield of the above dehydration reaction was 87%. As a result of measuring the metal content by ICP mass spectrometry, iron: 810 ppb, nickel: not detected, chromium: 560 ppb, ruthenium: not detected, and sodium: 320 ppb.

Example 4
(1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic acid (2.0 g) synthesized in Example 1 and distilled water (8.0 g) were placed in a 50 mL capacity Hastelloy autoclave with a stirrer, and the reaction was performed at 230 ° C. under a nitrogen atmosphere. A time isomerization reaction was performed.

  Furthermore, after cooling to 20 ° C., the precipitated crystals were filtered. The collected filtrate was dried under reduced pressure at 100 ° C. for 5 hours. As a result, 1.4 g of a light brown powder was obtained. The obtained light brown powder was methyl esterified and analyzed by gas chromatography. As a result, it was found that the powder was tt-CHTC and the purity was 87%. The molar yield at this time was 67%.

Example 5
First, tetramethyl (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylate was synthesized as follows with reference to Patent Document 2 (Example 4). Pyromellitic dianhydride (15 g) and methanol (50 g) were placed in a 200 mL volume SUS316 autoclave with a stirrer and esterified at 220 ° C. for 1 hour. This solution was charged with 0.3 g of 5% ruthenium / carbon and hydrogenated at a temperature of 130 ° C. and a hydrogen pressure of 10 MPa for 3 hours. Next, the catalyst was removed by filtration, and the resulting solution was dried with an evaporator to obtain a white solid. The obtained solid was washed with cold methanol and dried under reduced pressure to obtain 15.8 g of tetramethyl (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylate.

  Next, 10 g (0.032 mol) of tetramethyl (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylate, 1 g (0.019 mol) of sodium methoxide, and 50 g of dehydrated methanol were added to a flask having a volume of 200 mL. The suspension was refluxed in an oil bath at 80 ° C. for 4 hours.

  Furthermore, after cooling to 20 ° C., the suspension was filtered to collect a white powder, and then dried under reduced pressure at 50 ° C. for 5 hours. As a result, 2.5 g of white crystals were obtained. As a result of analysis by gas chromatography, it was found that the powder was tt-CHTC tetramethyl and the purity was 98%. The molar yield at this time was 25%.

Example 6
In a well-dried sealed reaction vessel with a stirrer, 5 mmol of p-phenylenediamine (hereinafter referred to as “PDA”) was dissolved in NMP, and 5 mmol of the tt-CHTCA powder obtained in Example 2 was gradually added to the solution. The mixture was stirred for 72 hours to obtain a uniform, transparent and viscous polyimide precursor solution. The solute concentration at this time is 12.2% by weight. This polyimide precursor solution did not precipitate or gel at all even when left at room temperature and at -20 ° C for one month, and showed extremely high solution storage stability. The intrinsic viscosity of the polyimide precursor measured in NMP at 30 ° C. was 1.60 / g, which was a high polymer.

  The polyimide precursor solution obtained by applying this polyimide precursor solution to a glass substrate and drying with hot air at 80 ° C. for 2 hours is 20 minutes at 200 ° C. in vacuum, 30 minutes at 250 ° C., and then 320 ° C. or 350 ° C. It imidized by heat-processing at 1 degreeC for 1 hour. As a result, a transparent and tough polyimide film having a film thickness of about 20 μm was obtained. The completion of imidization was confirmed from the infrared absorption spectrum. The polyimide film was not broken by a 180 ° bending test and showed flexibility. Table 1 shows the physical property values of the polyimide film. Glass transition temperature of 407 ° C., cutoff wavelength of 292 nm, transmittance at 400 nm of 64.6%, elongation at break of 30.8%, birefringence Δn = 0.0006, dielectric constant of 2.82 and excellent characteristics . Other physical properties are also shown in Table 1.

Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIGS. FIG. 9 is a diagram showing the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + PDA) obtained in this example, and FIG. 10 shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + PDA) obtained in this example. FIG.

Example 7
Polymerization was carried out according to the method described in Example 6 except that 4,4′-oxydianiline (hereinafter referred to as “ODA”) was used as the diamine instead of PDA, and a high intrinsic viscosity value (1. A polyimide precursor of 52 dL / g) was obtained. This was cast and imidized in the same manner as described in Example 6 to produce a polyimide film, and the physical properties were evaluated. The physical property values are shown in Table 1. It exhibited high Tg, high transparency, sufficient film toughness, and low birefringence.

  Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIG. 11 and FIG. FIG. 11 is a diagram showing an infrared absorption spectrum of the polyimide precursor (tt-CHTCA + ODA) obtained in this example, and FIG. 12 shows an infrared absorption spectrum of the polyimide thin film (tt-CHTCA + ODA) obtained in this example. FIG.

Example 8
Polymerization was carried out according to the method described in Example 6 except that 2,2′-bis (trifluoromethyl) benzidine (hereinafter referred to as “TFMB”) was used as the diamine instead of PDA. A polyimide precursor having an intrinsic viscosity value (2.43 dL / g) was obtained. A chemical imidization reagent (acetic anhydride / pyridine mixed solution, volume ratio 7/3) was dropped into the polyimide precursor solution, and the mixture was stirred at room temperature for 24 hours for imidization. This polyimide solution was dropped into a large amount of water to precipitate, washed, filtered and dried to isolate the polyimide as a powder. The completion of imidization was confirmed from the infrared absorption spectrum. This polyimide powder was dissolved in cyclopentanone to form a varnish, and cast and imidized under the same conditions as described in Example 6 to produce a polyimide film, and the physical properties were evaluated. The physical property values are shown in Table 1. It showed very high Tg, very high transparency, very high film toughness and very low dielectric constant. Since this polyimide has a trifluoromethyl group, it has high organic solvent properties, that is, solution processability, and showed high solubility at room temperature in NMP, DMAc, DMF, DMSO, cyclopentanone, cyclohexanone, and the like. Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIGS. FIG. 13 is a diagram showing an infrared absorption spectrum of the polyimide precursor (tt-CHTCA + TFMB) obtained in this example, and FIG. 14 shows an infrared absorption spectrum of the polyimide thin film (tt-CHTCA + TFMB) obtained in this example. FIG.

Example 9
Except for using 1,4-bis (4-aminophenoxy) benzene (hereinafter referred to as BAPB) in place of PDA as the diamine, polymerization was performed according to the method described in Example 6 and very high intrinsic viscosity was obtained. A polyimide precursor having a value (1.84 dL / g) was obtained. This was cast and imidized in the same manner as described in Example 6 to produce a polyimide film, and the physical properties were evaluated. The physical property values are shown in Table 1. It exhibited high Tg, high transparency, sufficient film toughness, and extremely low birefringence. Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIGS. FIG. 15 is a diagram showing an infrared absorption spectrum of the polyimide precursor (tt-CHTCA + BAPB) obtained in this example, and FIG. 16 shows an infrared absorption spectrum of the polyimide thin film (tt-CHTCA + BAPB) obtained in this example. FIG.

Example 10
Polymerization was carried out according to the method described in Example 6 except that 2,2-bis (4- (4-aminophenoxy) phenyl) propane (hereinafter referred to as “BAPP”) was used as the diamine instead of PDA. And a polyimide precursor having a very high intrinsic viscosity value (1.84 dL / g) was obtained. This was cast and imidized in the same manner as described in Example 6 to produce a polyimide film, and the physical properties were evaluated. The physical property values are shown in Table 1. It exhibited high Tg, high transparency, extremely high film toughness (elongation at break: 114%), and extremely low birefringence. Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIGS. FIG. 17 is a diagram showing an infrared absorption spectrum of the polyimide precursor (tt-CHTCA + BAPP) obtained in this example, and FIG. 18 shows an infrared absorption spectrum of the polyimide thin film (tt-CHTCA + BAPP) obtained in this example. FIG.

Example 11
Polymerization was carried out according to the method described in Example 6 except that bis (4- (4-aminophenoxy) phenyl) sulfone (hereinafter referred to as “BAPS”) was used instead of PDA as the diamine. A polyimide precursor having an intrinsic viscosity value (1.44 dL / g) was obtained. This was cast and imidized in the same manner as described in Example 6 to produce a polyimide film, and the physical properties were evaluated. The physical property values are shown in Table 1. It exhibited high Tg, very high transparency, high film toughness, and extremely low birefringence. Since this polyimide has a highly polar sulfone group, it has high organic solvent properties, that is, solution processability, and showed high solubility in NMP and the like at room temperature. Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIGS. FIG. 19 is a diagram showing an infrared absorption spectrum of the polyimide precursor (tt-CHTCA + BAPS) obtained in this example, and FIG. 20 shows an infrared absorption spectrum of the polyimide thin film (tt-CHTCA + BAPS) obtained in this example. FIG.

Example 12
Polymerization was carried out according to the method described in Example 6 except that 4,4′-methylenebis (cyclohexylamine) (hereinafter referred to as “MBCHA”) was used as the diamine instead of PDA. Although salt formation was observed at the initial stage of polymerization, the salt was gradually dissolved by stirring at room temperature to obtain a polyimide precursor having a uniform intrinsic viscosity (0.669 dL / g). This was cast and imidized in the same manner as described in Example 6 to produce a polyimide film, and the physical properties were evaluated. The physical property values are shown in Table 1. It exhibited very high Tg, very high transparency, sufficient film toughness and very low birefringence. Moreover, the infrared absorption spectrum of the polyimide precursor and the polyimide thin film was measured. The results are shown in FIG. 21 and FIG. FIG. 21 is a diagram showing an infrared absorption spectrum of the polyimide precursor (tt-CHTCA + MBCHA) obtained in this example, and FIG. 22 shows an infrared absorption spectrum of the polyimide thin film (tt-CHTCA + MBCHA) obtained in this example. FIG.

Example 13
In a fully dried sealed reaction vessel with a stirrer, 5 mmol of 4,4′-oxydianiline (hereinafter referred to as “ODA”) was dissolved in DMAc to prepare a reaction solution. In this reaction solution, cc-obtained by dehydrating 2.5 mmol of tt-CHTCA powder obtained in Example 2 and (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic acid prepared according to Non-Patent Document 2. By gradually adding a mixture with 2.5 mmol of CHTCA and stirring at room temperature for 72 hours, a uniform, transparent and viscous polyimide precursor solution was obtained. The intrinsic viscosity of the polyimide precursor measured at 30 ° C. in DMAc was 0.512 dL / g.

  The polyimide precursor solution obtained by applying this polyimide precursor solution to a glass substrate and drying it with warm air at 60 ° C. for 2 hours was vacuum-treated at 200 ° C. for 30 minutes, followed by 250 ° C. for 30 minutes, and further at 320 ° C. Imidization was performed by heat treatment for 1 hour. As a result, a transparent and tough polyimide film was obtained. The completion of imidization was confirmed from the infrared absorption spectrum. Each physical property includes a glass transition temperature of 336 ° C., a linear thermal expansion coefficient CTE = 53 ppm / K, a 5% weight loss temperature of 454 ° C. (in nitrogen) and 434 ° C. (in air), a transmittance at a cutoff wavelength of 294 nm and 400 nm. The refractive index was 80.8%, birefringence Δn = 0.0005, and the dielectric constant was 2.87 cal.

  Thus, if tt-CHTCA is contained in CHTCA having various isomers, a high molecular weight polyimide can be obtained without impairing the excellent physical properties of the polyimide using CHTCA which has been conventionally known. It was shown that it can be done.

[Comparative Example 1]
The (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic acid obtained in Example 1 was dehydrated in acetic anhydride at 130 ° C. to obtain (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic dianhydride. It was.

  In place of tt-CHTCA, (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic dianhydride was used, and TFMB was used as the diamine component, and the polyimide precursor was used in the same manner as described in Example 8. Was polymerized. However, the intrinsic viscosity value of the obtained polyimide precursor was as extremely low as 0.101 dL / g, and an attempt was made to form a film on a glass substrate using this varnish, but the film had numerous cracks and could not be formed. there were. This is because the molecular weight of the polyimide precursor was not sufficiently increased because tt-CHTCA was not used. In addition, casting was performed in the same manner as described in Example 6, imidization was performed, polyimide powder was dissolved in cyclopentanone to form a varnish, and an attempt was made to form a film. there were.

[Comparative Example 2]
A polyimide precursor was polymerized according to the method described in Comparative Example 1 except that PDA was used instead of TFMB as the diamine component. However, the intrinsic viscosity was as low as 0.33 dL / g, and although film formation was attempted, film formation was impossible as in Comparative Example 1. This is because the molecular weight of the polyimide precursor was not sufficiently increased because tt-CHTCA was not used.

[Comparative Example 3]
A polyimide precursor was polymerized according to the method described in Comparative Example 1 except that ODA was used instead of TFMB as the diamine component. However, the intrinsic viscosity value was a low value of 0.41 dL / g. This is because the molecular weight of the polyimide precursor was not sufficiently increased because tt-CHTCA was not used.

  Since tt-CHTCA according to the present invention is excellent as a raw material for polyimide, it can be widely applied in the chemical field concerning chemicals, fibers, reagents and the like.

2 is a diagram showing a three-dimensional structure of tt-CHTC obtained in Example 1. FIG. 1 is a diagram showing a ¹ H-NMR spectrum of tt-CHTC obtained in Example 1. FIG. 2 is a diagram showing a ¹³ C-NMR spectrum of tt-CHTC obtained in Example 1. FIG. 2 is a graph showing an infrared absorption spectrum of tt-CHTCA obtained in Example 2. FIG. 2 is a diagram showing a ¹ H-NMR spectrum of tt-CHTCA obtained in Example 2. FIG. 4 is a diagram showing a ¹³ C-NMR spectrum of tt-CHTCA obtained in Example 2. FIG. 4 is a diagram showing a powder X-ray diffraction pattern of tt-CHTC obtained in Example 2 before dehydration. FIG. 2 is a diagram showing an X-ray diffraction pattern of a tt-CHTCA hydrolyzate obtained in Example 2. FIG. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + PDA) obtained in Example 6. FIG. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + PDA) obtained in Example 6. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + ODA) obtained in Example 7. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + ODA) obtained in Example 7. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + TFMB) obtained in Example 8. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + TFMB) obtained in Example 8. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + BAPB) obtained in Example 9. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + BAPB) obtained in Example 9. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + BAPP) obtained in Example 10. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + BAPP) obtained in Example 10. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + BAPS) obtained in Example 11. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + BAPS) obtained in Example 11. It is a figure which shows the infrared absorption spectrum of the polyimide precursor (tt-CHTCA + MBCHA) obtained in Example 12. It is a figure which shows the infrared absorption spectrum of the polyimide thin film (tt-CHTCA + MBCHA) obtained in Example 12.

Claims (19)

  (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride.   1,2,4,5-cyclohexanetetracarboxylic dianhydride characterized by containing 50% or more of (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride.   (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid.   Of the cis-cis-cis isomers of 1,2,4,5-cyclohexanetetracarboxylic acid and the isomer mixture containing the cis-cis-cis isomer, at least one tetra salt is subjected to an isomerization reaction by heating (characterized in that 1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid production method.   Among the cis-cis-cis isomers of 1,2,4,5-cyclohexanetetracarboxylic acid and the isomer mixture containing the isomer, the isomerization reaction is performed by heating at least one tetraester (1S). , 2S, 4R, 5R) -cyclohexanetetracarboxylic acid production method.   The method for producing (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid according to claim 4, wherein a basic catalyst is used in the isomerization reaction.   7. The method for producing (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid according to claim 6, wherein an alkali metal alkoxide is used as the basic catalyst.   (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid comprising a step of dehydration reaction by heating in the presence of a dehydrating agent. Method for producing acid dianhydride.   A method for producing a tetracarboxylic dianhydride, comprising a step of dehydrating a (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid by heating in the presence of a dehydrating agent.   The tetracarboxylic dianhydride manufactured with the manufacturing method of Claim 9. General formula (1)
(In the above general formula (1), X represents a tetravalent cyclohexane group, and R represents a hydrogen atom, a trialkylsilyl group, or a linear, branched or cyclic alkyl group or alkoxyl group having 1 to 12 carbon atoms. A represents a divalent aromatic group or aliphatic group, and the configuration of X is represented by the following formula (2):
The bonding position between the X and the two amide groups and two carboxyl groups bonded to the X is represented by either the following formula (3) or (4).
(In formulas (3) and (4), Y represents two amide groups bonded to X, and Z represents two carboxyl groups bonded to X))
The polyimide precursor which has a repeating unit represented by these. General formula (5)
(In formula (5), X represents a tetravalent cyclohexane group, A represents a divalent aromatic group or aliphatic group, and the configuration of X is represented by the following formula (2).)
The polyimide which has a repeating unit represented by these.   A polyimide precursor obtained by using 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a synthesis raw material, wherein the 1,2,4,5-cyclohexanetetracarboxylic dianhydride is the claim 10. A polyimide precursor containing 50% or more of the above tetracarboxylic dianhydride.   A polyimide obtained using 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a synthesis raw material, wherein the 1,2,4,5-cyclohexanetetracarboxylic dianhydride is a tetramer according to claim 10. A polyimide containing 50% or more of carboxylic dianhydride.   A photosensitive resin composition comprising the polyimide precursor according to claim 11 or 13 and a photosensitive agent.   The photosensitive resin composition according to claim 15 is patterned on a substrate, developed after pattern exposure, and a pattern obtained by heating and curing after development is formed. A structure   A display substrate comprising the polyimide according to claim 12 or 14.   An interlayer insulating film for an integrated circuit, comprising the polyimide according to claim 12.   15. A liquid crystal alignment film comprising the polyimide according to claim 12 or 14.