JP2008163088A - Ester group-containing alicyclic tetracarboxylic anhydride and process for producing the same - Google Patents

Abstract

（式（１）中、Ａは芳香族基を含まない２価の基、好ましくは脂肪族基又は少なくとも１つのヘテロ元素を含む環状構造を含む基を示す。ｘ，ｙはそれぞれ独立に、０、１又は２、好ましくは０を示す。）
【選択図】図１Disclosed is a novel alicyclic polyesterimide having a low glass transition point and high solubility in an organic solvent by making a diol component at the time of synthesis of an ester group-containing alicyclic tetracarboxylic acid anhydride into a specific structure And an ester group-containing alicyclic tetracarboxylic acid anhydride which is a raw material thereof, and improves the processability of the resin.
An ester group-containing alicyclic tetracarboxylic acid anhydride represented by the following general formula (1). An alicyclic polyesterimide obtained by reacting this ester group-containing alicyclic tetracarboxylic acid anhydride with a diamine, followed by imidization.

(In the formula (1), A represents a divalent group containing no aromatic group, preferably an aliphatic group or a group containing a cyclic structure containing at least one hetero element. X and y are each independently 0 1 or 2, preferably 0.)
[Selection] Figure 1

Description

The present invention relates to an ester group-containing alicyclic tetracarboxylic anhydride and a method for producing the same, and in particular, a fat having a relatively low glass transition point, excellent solubility in an organic solvent, and excellent moldability. The present invention relates to an ester group-containing alicyclic tetracarboxylic acid anhydride capable of providing a cyclic polyesterimide and a method for producing the same.
The present invention also relates to a method for producing an alicyclic polyesterimide obtained using this ester group-containing alicyclic tetracarboxylic anhydride as a raw material and having excellent moldability.

  Polyimide has not only excellent heat resistance but also chemical resistance, radiation resistance, electrical insulation, excellent mechanical properties, etc., so it can be used for flexible printed circuit boards, tape automation bonding substrates, and semiconductors. Currently, it is widely used in various electronic devices such as protective films for elements and interlayer insulating films for integrated circuits. Polyimide is also a very useful material in terms of simplicity of production method, high film purity, and ease of improving physical properties, and functional polyimide material designs suitable for various applications have been made in recent years.

  Many polyimides are insoluble in organic solvents and do not melt above the glass transition point, so it is usually not easy to mold the polyimide itself. For this reason, polyimide is generally obtained by first reacting an aromatic tetracarboxylic dianhydride such as pyromellitic anhydride with an aromatic diamine such as diaminodiphenyl ether in an aprotic polar organic solvent such as dimethylacetamide to obtain a high molecular weight. A polyimide precursor having a polymerization degree is polymerized, this solution is formed into a film or the like, heated at a temperature of about 250 ° C. to 350 ° C., and dehydrated and closed (imidized) to form a film.

  Thermal stress generated in the process of cooling the polyimide / metal substrate laminate from the imidization temperature to room temperature often causes serious problems such as curling, film peeling and cracking. Recently, with the increase in the density of electronic circuits, multilayer wiring boards have come to be used. However, even if film peeling or cracking does not occur, the residual stress in the multilayer board can increase device reliability. Reduce significantly. For this reason, reduction of thermal stress has also been studied, but these low thermal stress resins have a problem of low solubility in solvents and poor operability.

  On the other hand, when polyimide is soluble in an organic solvent, a thermal imidization step is not required. Therefore, after applying a polyimide organic solvent solution (varnish) on a metal substrate, the solvent is removed at a temperature much lower than the thermal imidization temperature. It is only necessary to evaporate and dry, and it is possible to reduce the thermal stress in the metal substrate / insulating film laminate. However, there are only a limited number of polyimides that are soluble in organic solvents and put into practical use, and development of polyimides having various physical properties that are soluble in solvents is awaited.

  Furthermore, it is known that polyimide generally has a high water absorption rate. Water absorption in the insulating layer causes serious problems such as dimensional change of the insulating film and deterioration of electrical characteristics. It has been reported that the introduction of an ester bond into a polyimide skeleton is effective as a molecular design for realizing a low water absorption rate (Non-patent Document 1).

  In recent years, increasing the calculation speed of microprocessors and shortening the rise time of clock signals have become important issues in the information processing and communication fields. To that end, polyimide films used as insulating films It is necessary to lower the dielectric constant. Also, for high-density wiring and a multilayer substrate for shortening the electrical wiring length, it is advantageous in that the insulating layer can be made thinner as the dielectric constant of the insulating film is lower.

Introduction of a fluorine substituent into the skeleton is effective for lowering the dielectric constant of polyimide (Non-patent Document 2). However, the use of fluorinated monomers is disadvantageous in terms of cost.
In addition, replacing aromatic units with alicyclic units to reduce π electrons is an effective means for reducing the dielectric constant (Non-patent Document 3).

  However, it is not easy in terms of molecular design to obtain a polyimide having a low dielectric constant (3.0 or less as a target value), low water absorption and solvent solubility, and maintaining solder heat resistance. No practical material is known so far. Low dielectric constant polymer materials and inorganic materials other than polyimide are also being studied, but the present situation is that the required characteristics are not sufficiently satisfied in terms of dielectric constant, heat resistance and toughness.

  Furthermore, in recent years, the demand for a polyimide exhibiting high transparency in the visible light region is increasing due to the demand for development of optical material applications. In addition to this transparency, if a polyimide having heat resistance, solubility, and moderate toughness is obtained, it can be suitably used as a flexible substrate for liquid crystal displays and EL displays, and various optical property members used inside. However, at present, no material having such physical properties is known.

  In addition, for the purpose of performing through-hole formation and fine processing on polyimide as an insulating layer, a photosensitive polyimide system in which photosensitive performance is imparted to polyimide or its precursor itself has been actively studied. On the other hand, etching is performed on polyimide itself with a basic substance to form through holes. However, in the latter, since the etching rate of the polyimide film with alkali is usually slow, the etching solution is limited to a special basic substance such as ethanolamine, and even if ethanolamine is used, it cannot be applied to all polyimides. If a material having the above-mentioned required characteristics and easily etched by a general-purpose basic substance is developed, a material that is extremely useful in the industrial field can be provided. However, such a material is currently known. It is not done.

  Solving such conventional problems, it has both high glass transition point, high transparency, low water absorption and etching characteristics, the field of electronic materials such as electrical insulating films and laminates, flexible printed wiring boards in various electronic devices, Display devices such as liquid crystal display substrates, organic electroluminescence (EL) display substrates, electronic paper substrates, optical materials such as lenses, diffraction gratings and optical waveguides, semiconductors such as buffer coat films and interlayer insulation films, In addition, as an ester group-containing alicyclic tetracarboxylic acid anhydride that can provide a useful alicyclic polyesterimide in a solar cell substrate, a photosensitive material, etc., the present applicant has previously described a specific ester group-containing alicyclic group. A tetracarboxylic anhydride was proposed (Patent Document 1).

Since this tetracarboxylic acid anhydride has an alicyclic skeleton and contains an ester group, the polyimide resin synthesized from this acid dianhydride is highly transparent while maintaining high heat resistance. It has excellent properties such as properties, low dielectric properties, low water absorption, low thermal expansion, solvent solubility and etching properties. Therefore, resins for electronic materials such as electrical insulating films and flexible printed wiring boards, liquid crystal display substrates, organic electroluminescence (EL) display substrates, electronic paper substrates, solar cell substrates, and light-emitting diode sealing It can be used for an optical material such as an agent and an optical waveguide.
Japanese Patent Application No. 2006-308082 Proceedings of Macromolecules Conference, 53, 4115 (2004) Macromolecules, 24,5001 (1991) Macromolecules, 32, 4933 (1999)

  The ester group-containing alicyclic tetracarboxylic acid anhydride proposed in Patent Document 1 can be obtained by reacting the corresponding carboxylic acid chloride with diols. The physical properties of the alicyclic polyesterimide obtained from the anhydride as a raw material depend on the structure of the diols used for the synthesis of the ester group-containing alicyclic tetracarboxylic anhydride. For example, a polyesterimide obtained by combining an ester group-containing alicyclic tetracarboxylic acid anhydride obtained using hydroquinone as a diol with p-phenylenediamine or 4,4′-diaminodiphenyl ether as a diamine is glass transition. Since the point is as high as 200 ° C. or higher and the solubility in organic solvents is low, there is a problem in the molding process when a resin is used.

  The present invention solves such a problem. By making the diol component at the time of synthesizing an ester group-containing alicyclic tetracarboxylic acid anhydride into a specific structure, the glass transition point is low and organic An object of the present invention is to provide a novel alicyclic polyesterimide having high solvent solubility and an ester group-containing alicyclic tetracarboxylic acid anhydride which is a raw material thereof, and to improve the processability of the resin.

  As a result of intensive studies to solve the above problems, the present inventors have compared the glass transition point by using a diol that does not contain an aromatic group as a diol during the synthesis of an ester group-containing alicyclic tetracarboxylic anhydride. It was found that an alicyclic polyesterimide having excellent solubility in an organic solvent and excellent molding processability can be obtained.

  The present invention has been achieved based on the above findings, and the gist thereof is as follows.

（式（１）中、Ａは芳香族基を含まない２価の基を示す。ｘ，ｙはそれぞれ独立に、０、１又は２を示す。） [1] An ester group-containing alicyclic tetracarboxylic acid anhydride represented by the following general formula (1).

(In the formula (1), A represents a divalent group not containing an aromatic group. X and y each independently represents 0, 1 or 2.)

[2] The ester group-containing alicyclic tetracarboxylic acid according to [1], wherein A in the general formula (1) is an aliphatic group or a group containing a cyclic structure containing at least one hetero element Anhydride.

（式（２）中、ｚは０、１又は２を示す。） [3] The ester group-containing alicyclic group according to [1] or [2], wherein an acid chloride represented by the following general formula (2) is reacted with a diol in the presence of a basic substance. A method for producing tetracarboxylic anhydride.

(In the formula (2), z represents 0, 1 or 2.)

[4] A process for producing an alicyclic polyesterimide, comprising reacting the ester group-containing alicyclic tetracarboxylic acid anhydride and the diamine according to [1] or [2], followed by imidization. .

  According to the present invention, since the A part of the general formula (1) does not contain an aromatic group, the A part is preferably a group containing an aliphatic group or a cyclic structure containing at least one hetero element. Thus, while maintaining high transparency, the glass transition point is relatively low, the solubility in an organic solvent is excellent, and the alicyclic polyesterimide excellent in molding processability, and the ester group that is a raw material thereof A containing alicyclic tetracarboxylic acid anhydride can be provided.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.

[Ester group-containing alicyclic tetracarboxylic anhydride]
The ester group-containing alicyclic tetracarboxylic acid anhydride of the present invention is represented by the following general formula (1).

（式（１）中、Ａは芳香族基を含まない２価の基を示す。ｘ，ｙはそれぞれ独立に、０、１又は２を示す。）

(In the formula (1), A represents a divalent group not containing an aromatic group. X and y each independently represents 0, 1 or 2.)

  In the general formula (1), A may be any group that does not contain an aromatic group, and is not particularly limited. In particular, A may be a group containing an aliphatic group and / or a cyclic structure containing at least one hetero element. Preferred examples include the following.

<Aliphatic group>
An alkylene group having 2 to 10 carbon atoms such as an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group can be mentioned, but if the carbon number becomes larger than necessary, the heat resistance of the alicyclic polyesterimide is greatly reduced. Therefore, it preferably has 2 to 5 carbon atoms, particularly preferably 2 to 3 carbon atoms. These are not particularly limited even if they have a side chain, as long as they do not negatively affect the physical properties of the resin of the present invention. Among these, a linear aliphatic group is preferable.

<Group containing a cyclic structure containing at least one hetero element>
Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Examples of the group including a cyclic structure including at least one hetero element include those having a structure represented by the following general formula group (Z). .

<(Z) group>

(In the general formula group (Z), R represents hydrogen or any alkyl group, and the substitution position is any position that is structurally possible.)
Among these, the performance when an oxygen atom is used as a resin is good.
Furthermore, 2,3-tetrahydrofuranylene group, 1,2-tetrahydropyranylene group, and isosorbide group are preferable from the viewpoint of easy synthesis.

  In the general formula (1), x and y each independently represent 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

[Method for producing ester group-containing alicyclic tetracarboxylic anhydride]
The ester group-containing alicyclic tetracarboxylic anhydride of the present invention represented by the above general formula (1) comprises an acid chloride and a diol represented by the following general formula (2) in the presence of a basic substance. It can be obtained by reacting.

（式（２）中、ｚは０、１又は２を示す。）

(In the formula (2), z represents 0, 1 or 2.)

  In the general formula (2), z has the same meaning as x and y, preferably 0 or 1, and particularly preferably 0.

  The diol used for the synthesis of the ester group-containing alicyclic tetracarboxylic anhydride of the present invention is represented by HO-A-OH (A is the same as A in the general formula (1)). Specifically, examples of A as a linear aliphatic group include glycols having 2 to 10 carbon atoms such as ethylene glycol, propylene glycol and butylene glycol, and ester group-containing alicyclic tetracarboxylic acid anhydrides. 2,3-dihydroxytetrahydrofuran, 2,3-dihydroxytetrahydrothiophene, isosorbide and the like can be cited as examples in which the product is a group containing a cyclic structure containing at least one hetero element.

  These diols may be used alone or in a combination of two or more.

  Although there is no restriction | limiting in particular in the reaction method of such diol and an anhydride chloride, For example, it carries out as follows.

  First, there is a method for introducing a reaction reagent into a reaction vessel, in which a diol and a basic substance are dissolved in a solvent, and then anhydrous acid chloride dissolved in the same solvent is slowly dropped, or conversely If necessary, a method of dropping a mixed solution of a diol and a basic substance in an acid chloride dissolved in a solvent, a method of dropping a basic substance into a mixed solution of an acid chloride and a diol, and the like. It can be adopted.

  A white precipitate forms as the reaction proceeds. After filtering this, the precipitate is sufficiently washed with water to remove the generated hydrochloride, and the precipitate of the diester is heated and dried in vacuo, so that the target ester group-containing alicyclic tetracarboxylic acid anhydride is crude. The product can be obtained in good yield. Furthermore, the ester group containing alicyclic tetracarboxylic acid anhydride with which purity was improved can also be obtained by recrystallizing with a suitable solvent as needed.

  The amount of diol used is usually 0.6 equivalents or less, preferably 0.5 equivalents or less, with respect to anhydride chloride. If it is used more than this, a half ester or a half amide in which only one diol is esterified is produced, which is not preferable. The lower limit is not less than 0.3 equivalent, preferably not less than 0.45 equivalent. If it is less than this, it is not preferable because the acid chloride remains in the system. Usually, the diol is used in an amount of about 0.5 equivalent with respect to the acid chloride.

  Solvents that can be used when synthesizing ester group-containing alicyclic tetracarboxylic acid anhydrides by reacting anhydride chloride with diol are not particularly limited, but tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxy Ether solvents such as ethane-bis (2-methoxyethyl) ether, aromatic amine solvents such as picoline and pyridine, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane , Halogen-containing solvents such as chloroform, 1,2-dichloroethane, amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide Solvents, phosphorus-containing solvents such as hexamethylphosphonamide, dimethyls Sulfur-containing solvents such as sulfoxide, ester solvents such as γ-butyrolactone, ethyl acetate, butyl acetate, nitrogen-containing solvents such as 1,3-dimethyl-2-imidazolidinone, phenol, o-cresol , M-cresol, p-cresol, o-chlorophenol, m-chlorophenol, aromatic solvents having a hydroxyl group such as p-chlorophenol, and the like. These solvents may be used alone or in combination of two or more.

  The lower limit of the concentration of the solute in the reaction solution in the reaction for obtaining the ester group-containing alicyclic tetracarboxylic acid anhydride of the present invention is 1% by weight or more, preferably 10% by weight or more, preferably 50% by weight or less, preferably It is performed at 40% by weight or less. In consideration of the side reaction control and the precipitation filtration step, it is more preferably carried out in the range of 10 wt% to 40 wt%.

  When synthesizing the ester group-containing alicyclic tetracarboxylic acid anhydride of the present invention, the lower limit of the reaction temperature employed is −10 ° C. or higher, preferably −5 ° C. or higher, more preferably 0 ° C. or higher, and the upper limit is 30 ° C. Hereinafter, it is preferably performed at 20 ° C. or lower, more preferably at 10 ° C. or lower. If the reaction temperature is higher than 30 ° C., some side reactions occur, which may reduce the yield, which is not preferable.

  The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary. Moreover, reaction atmosphere is normally performed under nitrogen.

  The reaction vessel may be a closed type reaction vessel or an open type reaction vessel, but in order to keep the reaction system in an inert atmosphere, an open type vessel that can be sealed with an inert gas is used.

During the reaction, the base used is used to neutralize hydrogen chloride generated as the reaction proceeds.
Although the kind of base used in this case is not particularly limited, organic tertiary amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic bases such as potassium carbonate and sodium hydroxide can be used.

  The precipitate produced by the above reaction is a mixture of the target product and hydrochloride. In order to separate and remove the hydrochloride, it is possible to extract and dissolve the precipitate with chloroform, ethyl acetate, etc., and wash the organic layer with a separatory funnel, but simply washing the precipitate sufficiently with water, The hydrochloride can be completely removed. Determination of the removal of hydrochloride is performed by adding an aqueous silver nitrate solution to the cleaning solution and confirming the presence or absence of white precipitates of silver chloride.

  During the water washing operation, the tetracarboxylic anhydride is partially hydrolyzed and converted to tetracarboxylic acid, which can be easily converted into the tetracarboxylic anhydride of the present invention by heat treatment under reduced pressure. Can be returned.

In this case, the lower limit of the temperature employed is 50 ° C. or higher, preferably 120 ° C. or higher, and the upper limit is 250 ° C. or lower, preferably 200 ° C. or lower.
There is no lower limit on the degree of decompression employed for the ring closure treatment, and the upper limit is 0.1 MPa or less, preferably 0.05 MPa or less.

  In addition to the method of heating under reduced pressure as described above, a method of treating with an acid anhydride of an organic acid can also be employed as a method of re-ring closure when tetracarboxylic acid is obtained by hydrolysis. Examples of the acid anhydride of the organic acid used in this case include acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride, etc., but acetic anhydride is preferred because of easy removal when used in excess. Used for.

  The tetracarboxylic anhydride of the present invention thus obtained can be further purified. As a purification method in that case, recrystallization, sublimation, washing, activated carbon treatment, column chromatography and the like can be arbitrarily performed. These purification methods can be repeated or combined.

The solvent that can be used for recrystallization is not particularly limited as long as it is a solvent in which tetracarboxylic anhydride is dissolved.
Specifically, ether solvents such as tetrahydrofuran, dimethoxyethane, dioxane, nitrile solvents such as acetonitrile, aprotic polarities such as sulfolane, dimethyl sulfoxide, N-methylpyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, etc. Solvents, halogen solvents such as dichloromethane and 1,2-dichloroethane, and ester solvents such as ethyl acetate and butyl acetate can be used. Furthermore, a poor solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as heptane, hexane, or cyclohexane may be used in addition to these good solvents. When a poor solvent is added, the recovery rate of the target product can be increased.
During recrystallization, a dehydrating agent may coexist in order to prevent the acid anhydride ring from opening. In this case, examples of the dehydrating agent that can be used include acetic anhydride, propionic anhydride, maleic anhydride, and the like.

  The purity of the tetracarboxylic acid anhydride of the present invention thus obtained is usually 90% or more, preferably 95% or more, and more preferably as an area ratio of peaks obtained by analysis such as liquid high-performance chromatography with a differential refractive index detector. Is 98% or more.

  What is contained as an impurity is a monoester product in which only one of the diols is esterified, and this ring-closing agent when an acid anhydride such as acetic anhydride is used as a ring-closing agent during purification. Since these impurities contain one acid anhydride structure in the molecule, these impurities function as a polymerization terminator when polymerized with diamine, and therefore are removed from the tetracarboxylic acid anhydride as much as possible. It is necessary to keep. The content of an acid anhydride such as acetic anhydride contained in the tetracarboxylic acid anhydride is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 2 mol% or less. If these impurities are further present, there is a possibility that the degree of polymerization cannot be increased during the polymerization with diamine.

  Further, the synthesis yield of the ester group-containing alicyclic tetracarboxylic acid anhydride of the present invention by esterification of the above-mentioned acid chloride and diol is usually 10 mol% or more after purification, preferably 20 mol% or more, Preferably it is 30 mol% or more, More preferably, it is 50 mol% or more.

[Production of alicyclic polyesterimide]
The ester group-containing alicyclic tetracarboxylic anhydride of the present invention produced as described above is suitably used for the production of a polymer such as alicyclic polyesterimide, and has high characteristics due to excellent polymerization reactivity. The alicyclic polyesterimide can be produced.

  In order to produce an alicyclic polyesterimide, the tetracarboxylic acid anhydride purified as described above is reacted with substantially equimolar diamines in a polymerization solvent, thereby producing an alicyclic polyesterimide precursor. Manufacture the body. Here, tetracarboxylic acid anhydride may be used individually by 1 type, and may use 2 or more types together.

  In addition to the ester group-containing alicyclic tetracarboxylic dianhydride, it is possible to mix and use acid dianhydrides having other structures without limitation. In this case, examples of the acid dianhydride that can be used in addition to the ester group-containing alicyclic tetracarboxylic dianhydride include aromatic dianhydrides having one benzene ring such as pyromellitic acid, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride (a-BPDA), 3,3 ″, 4 4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2', 3,3'-benzophenone tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-oxydiphthalic anhydride (ODPA), bis (2,3-dicarboxyphenyl) -terdioic anhydride (a-ODPA), bis (3,4 -Dicarboxyphenyl) ether Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) propane dianhydride (BDCP), 2,2′-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (BDCF), 2,2′-bis (2,3- Aromatic dianhydrides having two benzene rings such as dicarboxyphenyl) hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalene Aromatic dianhydrides having a naphthalene skeleton such as tetracarboxylic dianhydride and 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride 1 Aromatic dianhydride having an anthracene skeleton such 2,5,6-anthracene tetracarboxylic acid dianhydride as an example.

On the other hand, examples of alicyclic acid anhydrides that can be additionally used include chained aliphatic tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic dianhydride and ethylenetetracarboxylic dianhydride. Acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4, 5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2. 2] octa-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride (BPDA hydrogenated product), 2, 3,5-tricarboxycyclopen Diacetate dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8- And tetracarboxylic dianhydride having an alicyclic structure such as tetracarboxylic dianhydride.
The use ratio of these acid dianhydrides and the tetracarboxylic acid anhydride of the present invention can be arbitrarily set depending on the physical properties of the resin to be obtained, but the use amount of the tetracarboxylic acid anhydride of the present invention is 5 mol%. The above is preferable, and it is more preferable to use 10 mol% or more.

  The diamine used for producing the alicyclic polyesterimide precursor according to the present invention is freely selected as long as the polymerization reactivity during the production of the precursor and the required characteristics of the alicyclic polyesterimide are not significantly impaired. Is possible. Specific examples of diamines that can be used include aromatic diamines such as 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, and 3,3′-bistrifluoromethyl-4,4′-diaminobiphenyl. 3,3′-bistrifluoromethyl-5,5′-diaminobiphenyl, bis (trifluoromethyl) -4,4′-diaminodiphenyl, bis (fluorinated alkyl) -4,4′-diaminodiphenyl, dichloro- 4,4′-diaminodiphenyl, dibromo-4,4′-diaminodiphenyl, bis (fluorinated alkoxy) -4,4′-diaminodiphenyl, diphenyl-, 4′-diaminodiphenyl, 4,4′bis (4 -Aminotetrafluorophenoxy) tetrafluorobenzene, 4,4'-bis (4-aminotetra (Luorofoxy) octafluorobiphenyl, 4,4′-binaphthylamine, o-, m-, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4- Diaminodurene, dimethyl-4,4′-diaminodiphenyl, dialkyl-4,4′-diaminodiphenyl, dimethoxy-4,4′-diaminodiphenyl, diethoxy-4,4′-diaminodiphenyl, 4,4′-diamino Diphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 3,3 ′ -Diaminobenzophenone, 1,3-bis (3-aminophen Xy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-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, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-amino-2-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- ( 3-amino-5-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2 , 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2 bis (3-amino-4-methylphenyl) hexafluoropropane, 4,4′-bis (4-aminophenoxy) Examples include octafluorobiphenyl and 4,4′-diaminobenzanilide, and two or more of these can be used in combination.

  Examples of the aliphatic diamine include 4,4′-methylenebis (cyclohexylamine), isophoronediamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 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-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 1,3-propanediamine 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenedia Emissions, 1,7 heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylenediamine, and the like. Two or more of these may be used in combination.

Furthermore, siloxane group-containing diamines such as 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane can also be used.
Among these diamines, aromatic diamines include mononuclear phenylenediamine compounds such as o-, m-, and p-phenylenediamine, 4,4'-diaminodiphenyl, 4,4'-diaminodiphenylsulfone, 4,4. Diaminodiphenyl compounds such as' -diaminodiphenylmethane and 4,4'-diaminodiphenyl ether are preferable. Among them, p-phenylenediamine, 4,4'-diaminodiphenyl ether, More preferred is 4,4′-diaminodiphenyl. As the aliphatic diamine, alicyclic diamines such as 4,4′-methylenebis (cyclohexylamine), trans-1,4-diaminocyclohexane, isophoronediamine and the like are preferable because they have a ring structure and are easily available. The resin from which trans-1,4-diaminocyclohexane is obtained is more preferable because of good physical properties.
These may be used alone or in combination of two or more.

  The ratio of tetracarboxylic acid anhydride to diamine is preferably 1: 0.8 to 1.2 in terms of molar ratio. As in the normal polycondensation reaction, the closer the molar ratio is to 1: 1, the higher the molecular weight of the polyamic acid obtained.

If the reaction temperature is too low, the solubility of the reagent is lowered, a sufficient reaction rate cannot be obtained, and if it is too high, it is difficult to control the progress of the reaction. The lower limit is −20 ° C., preferably −10 ° C., more preferably 0 ° C., and the upper limit is 150 ° C., preferably 100 ° C., more preferably 60 ° C.
Although the reaction time can be adopted without any particular limitation, in order to achieve a sufficient reagent conversion rate, the lower limit is 10 minutes, preferably 30 minutes, more preferably 1 hour, and the upper limit is not particularly limited, but the reaction is completed. There is no need to extend the reaction time more than necessary. For example, 100 hours, preferably 50
Time, more preferably 30 hours, is employed.

  The polymerization reaction is performed using a solvent. As the solvent used in this case, there is no problem as long as the diamine as the raw material monomer and the alicyclic tetracarboxylic acid of the present invention do not react with the solvent, and these raw materials dissolve, and the structure is particularly limited. Not. 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, lactam solvents such as caprolactam, ether solvents such as dioxane, glycol solvents such as triethylene glycol, m- Phenolic solvents such as cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, 4-methoxyphenol, 2,6-dimethylphenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane , Dimethyl Sulfoxide, tetramethyl urea are preferably employed. In addition, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl 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 A solvent etc. can also be added and used. Of these, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and γ-butyrolactone are preferred because of the high solubility of the raw materials.

  The solvent is preferably used in such an amount that the weight concentration of the total amount of tetracarboxylic anhydride and diamine as raw materials falls within the following range. That is, the concentration is 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, although the upper limit is not particularly limited, but from the viewpoint of solubility of tetracarboxylic anhydride, it is 80% by weight or less. Preferably, 50% by weight or less, more preferably 30% by weight or less is employed. By performing polymerization in the concentration range of this tetracarboxylic acid anhydride, a polyimide precursor solution having a uniform and high degree of polymerization can be obtained. In order to impart film toughness to the target polyesterimide, the degree of polymerization of the polyesterimide precursor is preferably as high as possible. When polymerization is performed at a concentration lower than the above concentration range, the degree of polymerization of the polyimide precursor is sufficient. Is not preferable, and the finally obtained polyimide film may be brittle. When an alicyclic diamine is used as the diamine, a higher polymerization concentration requires a longer polymerization time until the formed salt dissolves and disappears, which may lead to a decrease in productivity.

If necessary, inorganic salts may be used as a catalyst in the production of the precursor. The inorganic salts used in this, for example LiCl, NaCl, alkali metal halide such as LiBr, alkaline earth metal halides such as CaCl _2, metal halide such as ZnCl ₂ and the like. Of these, _LiCl, metal chlorides such as CaCl 2, ZnCl ₂ is particularly preferred.
The reaction is preferably carried out with stirring during the process.

  The intrinsic viscosity of the alicyclic polyesterimide precursor of the present invention thus obtained is not particularly limited, but as a preferred intrinsic viscosity, the lower limit is 0.3 dL / g, preferably 0.5 dL / g, Preferably, it is 0.7 dL / g. On the other hand, the upper limit is 5.0 dL / g, preferably 3.0 dL / g, more preferably 2.0 dL / g. Intrinsic viscosity is measured by the method described in the Examples section below.

  Examples of the method for synthesizing the alicyclic polyesterimide include (i) a method obtained from an alicyclic polyesterimide precursor and (ii) a method obtained without using an alicyclic polyesterimide precursor. And (i) As a method obtained from an alicyclic polyesterimide precursor, there are a heating imidization method and a chemical imidization method. However, the production method of the alicyclic polyesterimide of the present invention is not particularly limited to the production method described below.

(I) Method Obtained from Alicyclic Polyesterimide Precursor The alicyclic polyesterimide of the present invention can be produced by subjecting the alicyclic polyesterimide precursor obtained by the above method to a cyclization imidization reaction. it can.
At this time, the manufacturable form of the alicyclic polyesterimide is a film, a powder, a molded body and a solution.

  An alicyclic polyesterimide film can be produced, for example, as follows. First, the polymerization solution (varnish) of the alicyclic polyesterimide precursor is cast and applied onto a substrate such as glass, copper, aluminum, silicon, a quartz plate, a stainless plate, or a Kapton film. As a method of coating, the alicyclic polyesterimide solution obtained as described above is dropped onto the above-mentioned substrate and the solution is stretched on a support having a fixed height, thereby extending the solution to a uniform height. Can be applied. At this time, it may be performed using a device such as a doctor blade. As other coating methods, any method capable of coating the solution with a predetermined thickness, such as a spin coating method, a printing method, and an ink jet method, can be employed without any limitation.

  Since the coating film thus applied contains a solvent, it is then dried. The lower limit of the drying temperature employed at that time is usually 20 ° C., preferably 40 ° C., more preferably 60 ° C. On the other hand, the upper limit is 200 ° C, preferably 150 ° C, more preferably 100 ° C.

The drying time can be used without particular limitation as long as the solvent is removed to some extent, but the lower limit is 10 minutes, preferably 30 minutes, more preferably 1 hour, and the upper limit is not particularly limited, but 50 hours, preferably 30 Time, more preferably 10 hours, is employed.
Drying may be performed under reduced pressure. The degree of reduced pressure employed at that time is usually 0.05 MPa or less, preferably 0.01 MPa or less, more preferably 0.001 MPa or less.

  The dried alicyclic polyesterimide precursor film thus obtained is imidized by heating on a substrate in a vacuum, in an inert gas such as nitrogen, or in air at a high temperature. This method is called heat imidization.

  The lower limit of the temperature employed at this time is 180 ° C., preferably 200 ° C., more preferably 250 ° C. On the other hand, the upper limit is 500 ° C., preferably 400 ° C., more preferably 350 ° C. If the heating temperature is 180 ° C. or less, the cyclization reaction of the cyclization imidation reaction is incomplete, which is not preferable, and if it is too high, the produced alicyclic polyimide ester film may be colored. Therefore, it is not preferable. The imidization is preferably performed in a vacuum or in an inert gas, but may be performed in air if the temperature of the imidization reaction is not too high. The degree of reduced pressure employed when the heat imidization is performed under reduced pressure is usually 0.05 MPa or less, preferably 0.01 MPa or less, and more preferably 0.001 MPa or less.

  The time for which the cyclization imidation proceeds sufficiently is adopted as the heating time, but usually the lower limit is 5 minutes, preferably 10 minutes, more preferably 20 minutes, and the upper limit is not particularly limited, but 20 hours, preferably 10 hours, more preferably 5 hours are employed.

[Physical properties of alicyclic polyesterimide]
The alicyclic polyesterimide of the present invention thus produced includes DMAc, N-methyl-2-pyrrolidone, N, N-dimethylformamide, γ-butyrolactone, cyclohexanone and the like as shown in Example 3 described later. The organic solvent exhibits high solubility at room temperature, and its glass transition point Tg (° C.) is usually 100 ° C., preferably 110 ° C., more preferably 120 ° C., and the upper limit is usually 200 ° C., preferably 190 ° C. C., more preferably within the range of 180.degree. C., and excellent moldability.

  In addition, the glass transition point of an alicyclic polyesterimide is measured by the method described in the term of the below-mentioned Example.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples, unless the summary is exceeded.
In the following, the NMR spectrum of tetracarboxylic anhydride, mass spectrometry, and the method for measuring the glass transition point of polyimide are as follows.

<Proton NMR ( ¹ H-HMR) spectrum>
The product was dissolved in deuterated dimethyl sulfoxide and measured using a proton resonance frequency 400 MHz NMR spectrometer.

<Mass spectrometry>
Measurement was performed by ionization mode FAB method using a mass spectrometer (JMS-700) manufactured by JEOL Ltd.

<Glass dislocation point>
Using a differential scanning calorimeter (DSC 6220) manufactured by SII NanoTechnology, the heating rate was 10 ° C./min. DSC measurement was performed under the conditions described above to determine the glass transition point.

[Example 1]
The synthesis of nuclear hydrogenated trimellitic anhydride chloride was carried out as follows.
Under nitrogen flow, 40.91 g (0.189 mol) of nuclear hydrogenated trimellitic acid, 40.6 mg (0.56 mmol) of N, N′-dimethylformamide, and 200 ml of toluene were added to a 500 mL four-necked flask. Dissolved. To this was added 64.35 g (0.541 mol) of thionyl chloride, and the mixture was reacted at 60 ° C. for 4.5 hours in a nitrogen atmosphere. After the reaction, excess thionyl chloride and toluene were distilled off under reduced pressure, and the contents were concentrated to about 100 g. To this solution was added 300 ml of hexane to precipitate a solid, which was separated by filtration and vacuum dried at room temperature for 5 hours to obtain 32.9 g (yield 82.2%) of nuclear hydrogenated trimellitic anhydride chloride.

  Next, 0.421 g (6.8 mmol) of ethylene glycol and 1.10 g (13.8 mmol) of pyridine were dissolved in 9 mL of tetrahydrofuran in a 50 mL three-necked flask. In this, 3.0 g (13.8 mmol) of nuclear hydrogenated trimellitic anhydride chloride dissolved in 6 mL of tetrahydrofuran was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour and further at 50 ° C. for 2 hours. After the reaction, pyridine hydrochloride was removed by filtration, and the filtrate was concentrated. The concentrate was dissolved in 20 ml of ethyl acetate, washed 3 times with 5 ml of water, and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated and the resulting oil was recrystallized with 5 ml of toluene / ethyl acetate (1/1) to obtain 1.79 g (yield 62.5%) of the product as a white powder.

The compound ^{1 H-NMR} spectrum and mass spectrum, it is the product obtained is ethylene glycol hydrogenated trimellitic acid diester which is an object of the structure of the following formula (1A) was confirmed.

GC-MS (FAB method): m / z = 423 corresponding to (M + H) ⁺ was confirmed.
¹ H-NMR (4000 MHz; DMSO-d ₆ ):
1.46-1.57 (m, 2H),
1.43-1.61 (m, 4H),
1.96-2.00 (m, 2H),
2.27-2.47 (m, 6H),
3.20-3.26 (m, 4H),
4.30 (s, 4H)

[Example 2]
In a 50 mL three-necked flask, 0.690 g (6.76 mmol) of erythritan and 1.07 g (13.5 mmol) of pyridine were dissolved in 9 mL of tetrahydrofuran. In this, 3.0 g (13.8 mmol) of nuclear hydrogenated trimellitic anhydride chloride dissolved in 6 mL of tetrahydrofuran was dropped at room temperature. After completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours and further at 50 ° C. for 2 hours. After the reaction, pyridine hydrochloride was removed by filtration, and the filtrate was concentrated. The concentrate was dissolved in 30 ml of ethyl acetate, washed 3 times with 10 ml of water, and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to obtain 3.00 g (yield 95.7%) of a white solid.

This compound was confirmed to be the target erythritan hydrogenated trimellitic acid diester having the structure of the following formula (1B) by ¹ H-NMR spectrum and mass spectrometry spectrum.

GC-MS (FAB method) confirmed :( M + ^H) corresponding to ⁺ m / z = 465
¹ H-NMR (400 MHz; DMSO-d6):
1.38-1.56 (m, 2H),
1.54-1.73 (m, 2H),
1.71-1.86 (m, 2H),
1.89-2.02 (m, 2H),
2.26-2.45 (m, 6H),
3.09-3.31 (m, 4H),
3.72-3.84 (m, 2H),
4.01-4.15 (m, 2H),
5.24-5.38 (m, 2H)

[Example 3]
An alicyclic polyesterimide was produced using ethylene glycol hydrogenated trimellitic acid ester as a raw material.
Under a nitrogen stream, 99.2 mg (0.495 mmol) of 4,4′-diaminodiphenyl ether (hereinafter abbreviated as ODA) and 850 mg of N, N-dimethylacetamide (hereinafter abbreviated as DMAc) were added to a 10 mL flask and stirred at room temperature. And dissolved. To this, 214.5 mg (0.507 mmol) of ethylene glycol hydrogenated trimellitic acid diester synthesized in Example 1 was added and stirred for 69 hours. Thereafter, 5.4 g of DMAc, 560 mg of acetic anhydride and 277 mg of pyridine were added and reacted at room temperature for 1 hour and subsequently at 50 ° C. for 2 hours. The contents were poured into 100 ml of water, the precipitate was filtered off, washed with methanol, and then vacuum dried at 100 ° C. for 5 hours to obtain 257 mg of polyesterimide powder.

The synthesized polyesterimide powder was dissolved in DMAc to a 20% solids concentration and applied on a glass plate. The glass plate was heated at 80 ° C. for 1 hour and at 150 ° C. for 1 hour to obtain a polyesterimide film. The glass transition point was 130 ° C.
Moreover, it showed high solubility at room temperature in organic solvents such as DMAc, N-methyl-2-pyrrolidone, N, N-dimethylformamide, γ-butyrolactone, and cyclohexanone, and it was confirmed that the processability was good.

  The polyesterimide obtained in Example 3 has the following structure. The NMR spectrum of this product measured in DMSO (dimethyl sulfoxide) is shown in FIG.

[Comparative Example 1]
An alicyclic polyimide was produced from hydroquinone hydrogenated trimellitic acid ester as a raw material.
Under a nitrogen flow, 13.81 g (125 mmol) of hydroquinone and 20.24 g (256 mmol) of pyridine were dissolved in 160 ml of tetrahydrofuran in a 500 mL four-necked flask and cooled to 0 ° C. with an ice bath. A solution obtained by dissolving 55.43 g (256 mmol) of nuclear hydrogenated trimellitic anhydride chloride in 110 mL of tetrahydrofuran was added dropwise thereto. After completion of the dropwise addition, the mixture was returned to room temperature and reacted for 15 hours. After the reaction, the precipitated white solid was separated by filtration and washed 4 times with 40 ml of water to remove the hydrochloride. This was vacuum dried at 120 ° C. to obtain 47.8 g (yield 81.0%) of the product.

  To a 1 L three-necked flask, 23.9 g of hydroquinone hydrogenated trimellitic acid diester obtained in Example 1, 200 ml of acetic anhydride and 300 ml of acetic acid were added and dissolved at 140 ° C. This was cooled at room temperature, and the precipitated solid was filtered off and then vacuum dried at 150 ° C. to obtain 13.7 g of the desired product.

  To a 50 mL three-necked flask, 0.801 g (4.00 mmol) of ODA and 10.75 g of DMAc were added and stirred at room temperature to dissolve. To this was added 1.88 g (4.00 mmol) of the purified tetracarboxylic anhydride, and the mixture was stirred for 1 hour. Next, after diluting with 6.39 g of DMAc, the mixture was continuously stirred for 16 hours. The intrinsic viscosity of the alicyclic polyesterimide precursor was 1.99 dL / g, which was a very high polymer. Thereafter, 13.68 g of DMAc was added for dilution, and 5 ml of acetic anhydride and 2.5 ml of pyridine were added and reacted at 100 ° C. for 4 hours. After cooling, the content was poured into 200 ml of methanol, and the precipitate was separated by filtration, washed with methanol and then vacuum dried at 100 ° C. for 5 hours to obtain 2.18 g of polyimide powder.

  The synthesized polyesterimide powder was dissolved in DMAc to a 20% solids concentration and applied on a glass plate. The glass plate was heated at 80 ° C. for 1 hour and at 200 ° C. for 1 hour to obtain a good polyesterimide film.

  The polyesterimide obtained in Comparative Example 1 has the following structure, and has a glass transition point of 220 ° C. and dissolved in DMAc and N-methylpyrrolidone, but does not dissolve in cyclohexanone and has poor processability. Met.

4 is an NMR spectrum chart of the polyesterimide obtained in Example 3 measured in DMSO.

Claims (4)

An ester group-containing alicyclic tetracarboxylic acid anhydride represented by the following general formula (1).

(In the formula (1), A represents a divalent group not containing an aromatic group. X and y each independently represents 0, 1 or 2.)   The ester group-containing alicyclic tetracarboxylic acid anhydride according to claim 1, wherein A in the general formula (1) is an aliphatic group or a group containing a cyclic structure containing at least one hetero element. The ester group-containing alicyclic tetracarboxylic acid anhydride according to claim 1 or 2, wherein an acid chloride represented by the following general formula (2) and a diol are reacted in the presence of a basic substance. Manufacturing method.

(In the formula (2), z represents 0, 1 or 2.)   A method for producing an alicyclic polyesterimide, wherein the ester group-containing alicyclic tetracarboxylic acid anhydride according to claim 1 or 2 is reacted with a diamine and then imidized.

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