JP2008297231A - Hydroxyamide group-containing alicyclic polyimide, precursor of the same, positive type photosensitive resin composition by using them and their cured materials - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polybenzoxazole imide film useful as a protecting film of a semiconductor element and plastic substrate plate for a display by using a hydroxyamide group-containing alicyclic polyimide having a high transmission at an i-line (365 nm), or its precursor. <P>SOLUTION: This polybenzoxazole imide film is formed by performing pattern exposure and alkali development of the film of a positive type photosensitive resin composition containing a diazonaphthoquinone-based photosensitizer in the hydroxyamide group-containing alicyclic polyimide containing a recurring unit expressed by general formula (4) [wherein, A is a tetravalent aromatic group; and B is a divalent aromatic or aliphatic group] or its precursor, and then heating. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition comprising a diazonaphthoquinone photosensitizer in a hydroxyamide group-containing transparent polyimide having high i-line (365 nm) transmittance or a precursor thereof, and the positive photosensitive resin. Polybenzoxazole imide useful as a protective film for semiconductor elements and plastics for flexible liquid crystal displays (LCDs), which is obtained through an alkali development / washing / heat dehydration cyclization reaction step after pattern exposure of the conductive resin composition, The present invention relates to a method for producing a fine pattern of benzoxazole imide.

  In recent years, the importance of polyimide as a heat-resistant insulating material in electronic devices has been increasing. Polyimide has not only excellent heat resistance, but also chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties, so it can be used for flexible printed circuit (FPC) substrates, tape automation bonding (TAB). ) Base materials, chip-on-film (COF) base materials, protective films for semiconductor elements, interlayer insulating films for integrated circuits, and the like.

  Polyimide is obtained by polymerizing a solvent-soluble precursor (polyamic acid) by subjecting diamine and tetracarboxylic dianhydride to a non-catalytic equimolar polyaddition reaction in a solvent such as N-methyl-2-pyrrolidone. (Varnish) can be easily produced by solution casting film formation, drying, and heat dehydration cyclization (imidation reaction). In addition to the simplicity of the manufacturing process, since the film purity is extremely high, it is suitable for semiconductor applications that hate residual halogens, metal ions, and the like that may cause a decrease in electrical characteristics. Further, it is advantageous in that it is easy to improve physical properties using various available monomers, and it is easy to cope with demand characteristics that are increasingly diversified in recent years.

  As a protective coating material on the surface of a semiconductor chip, the chip is protected from curing shrinkage of a sealing material such as an epoxy resin, the chip is protected from thermal shock and rapid thermal expansion stress of the sealing material in the solder reflow process, on the chip Prevention of cracks when forming an inorganic passivation film, prevention of soft errors due to α-ray shielding from trace amounts of uranium and thorium contained in the inorganic filler in the sealing material, interlayer insulation of multilayer wiring circuits, wiring by flattening Currently, heat-resistant polyimide is used for the purpose of preventing wire breakage.

  The protective coating material is subjected to fine processing such as via hole formation by plasma etching or alkali etching on the bonding pad portion. A dry method such as plasma etching is generally excellent in resolution, but is expensive in terms of equipment, so that wet etching using an alkaline aqueous solution or the like is simpler.

  Conventionally, microfabrication of a polyimide film has been performed by forming a photoresist layer on the polyimide film and etching the exposed portion with hydrazine or strong alkali, but the polyimide or its precursor itself has photosensitive performance. By using the photosensitive polyimide to which is added, the microfabrication process of polyimide is greatly shortened, and it becomes possible to dramatically increase the semiconductor manufacturing speed and the yield rate.

  For this purpose, a positive photosensitive polyimide capable of alkali development in which a diazonaphthoquinone photosensitizer is dispersed in a polyamic acid film as a polyimide precursor has been studied. However, the carboxyl group in the polyamic acid has a low pKa value of 4 to 5, and the alkali solubility of the polyamic acid in the aqueous solution of tetramethylammonium hydroxide (TMAH) that is usually used as a developing solution in the semiconductor manufacturing process is originally too high. For this reason, it has been pointed out that a sufficient solubility difference between the exposed part and the unexposed part is difficult to obtain and is not suitable for high-resolution fine processing.

  In recent years, from the viewpoint of high resolution and precise control of pattern shape, a phenolic hydroxy group-containing polybenzoxazole precursor having an appropriate pKa value (about 10) instead of a polyimide precursor unsuitable for alkali development as described above A positive photosensitive polybenzoxazole system in which a diazonaphthoquinone photosensitizer (hereinafter referred to as DNQ) is combined using a photocatalyst has attracted attention.

  Polybenzoxazole (hereinafter referred to as PBO) obtained by thermal ring-closing reaction of polyhydroxyamide (hereinafter referred to as PHA), which is a polybenzoxazole precursor, is superior to polyimide in addition to having heat resistance equivalent to that of polyimide. It is a material excellent as a semiconductor protective coating material in that it has low water absorption.

  However, the production process of PHA, which is a PBO precursor, is not as simple as the polyamic acid system, which is a polyimide precursor. In the polyamic acid system, a high polymer can be obtained very easily without catalyst and at room temperature by an equimolar polyaddition reaction of tetracarboxylic dianhydride and diamine in an amide solvent such as N-methyl-2-pyrrolidone (NMP). On the other hand, in the PHA system, the dicarboxylic acid is first converted into an active acyl, which is polycondensed with bis (o-aminophenol) under heating conditions, and further, a PHA isolation / generation process is required. Is more complicated.

  In addition, bis (o-aminophenol) is commercially available as 3,3′-dihydroxybenzidine (HAB) or 2,2-bis (3-amino-4-hydroxyphenyl) hexa In contrast to polyimides, which are limited to fluoropropane (BAHF) and have a wide selection range of monomers, it is difficult to meet the increasingly demanding characteristics of semiconductor materials.

  Moreover, in many cases, PHA which is a PBO precursor has lower solubility in a solvent than polyamic acid which is a polyimide precursor. This is because the polyamic acid has a carboxyl group that is advantageous for solvation in the side chain, and the amide bond of the main chain generated in the polymerization process becomes a para / metarandom chain, so it is easily soluble in the solvent. On the other hand, in the PHA system, the side chain is a hydroxy group that is disadvantageous for solvation, and the amide bond does not become a random chain.

  As described above, there are advantages and disadvantages between the photosensitive polyimide system and the photosensitive PBO system, but the ease of the polymerization process and the ease of improving physical properties (various available monomers), which are the advantages of the polyimide system, If there is a heat-resistant material having both high-resolution processing ease, which is an advantage of the PBO system, it can provide an extremely useful material in the industrial field, but such a photosensitive heat-resistant material is hardly known. Is the current situation.

For example, it is known that a clear positive pattern can be formed by using a photosensitive resin composition in which a phenolic hydroxy group-containing polyimide containing a repeating unit represented by the following formula (6) is combined with DNQ. (For example, see Non-Patent Document 1 and Non-Patent Document 2).
(In formula (6), X is a tetravalent aromatic group.)

  The phenolic hydroxy group-containing polyimide containing a repeating unit represented by the formula (6) performs equimolar polyaddition reaction with tetracarboxylic dianhydride using bis (o-aminophenol) as a diamine component. Thus, a hydroxyl group (OH group) -containing polyamic acid is first polymerized and then subjected to a thermal imidization reaction. However, unlike a normal PBO precursor, after forming a positive pattern by alkali development, the phenolic OH group remains without being extinguished even when heat-treated. In semiconductor applications such as buffer coat films, it is used for a long time as a permanent protective film for integrated circuits. Therefore, in addition to problems such as ion migration triggered by the presence of phenolic OH groups and an increase in water absorption, various unexpected functions May cause serious problems.

Using a tetracarboxylic dianhydride represented by the following formula (7), a polyimide precursor containing a repeating unit represented by the following formula (8) is polymerized, and the obtained polyimide precursor or the polyimide precursor is obtained. A technique for forming a positive pattern using a photosensitive resin composition in which a compound containing a repeating unit represented by the following formula (9) obtained by imidizing a body is combined with DNQ is disclosed (for example, Patent Document 1).
(In formula (8) and formula (9), R represents a divalent aromatic group.)

  However, in the hydroxyamide group-containing tetracarboxylic dianhydride represented by the above formula (7), an electron donating bis (o-aminophenol) residue bonded through an amide bond and an electron withdrawing property In addition to the intramolecular charge transfer interaction that occurs based on the fact that both of the trimellitic anhydride residues are aromatic groups, it is easy to color due to partial oxidation of the phenolic OH group, so it can be obtained using this The resulting polyimide precursors and polyimide cast films are often highly colored, leading to undesirable results such that little i-line is transmitted.

  If a strong electron-withdrawing group is introduced onto bis (o-aminophenol), in principle, coloring due to intramolecular charge transfer interaction of the hydroxyamide group-containing tetracarboxylic dianhydride is suppressed to some extent in principle. However, a low-colored hydroxyamide group-containing tetracarboxylic dianhydride obtained using bis (o-aminophenol) other than BAHF is not known.

  If the molecular structure of the hydroxyamide group-containing tetracarboxylic dianhydride can be modified to suppress the intramolecular charge transfer interaction, the sensitivity of the photosensitive resin composition can be improved (i-line exposure (Reduction of irradiation time) is expected.

  When applying a positive photosensitive resin composition combining a polyimide precursor or polybenzoxazole precursor and DNQ as a material for a buffer coating film of a semiconductor element, it is usually heated at a high temperature after forming a positive pattern by alkali development. A step of curing (thermal cyclization) is performed. In particular, polybenzoxazole precursor systems generally require high-temperature treatment at 300 ° C. or higher to complete the thermal cyclization reaction, so it is difficult to apply these systems to buffer coating films from the viewpoint of protecting semiconductor devices. It may become. Therefore, researches on polybenzoxazoles that can be thermally cyclized at lower temperatures have been actively conducted.

  It has been reported that the thermal cyclization reaction of a polybenzoxazole precursor is significantly reduced in temperature by an acid catalyst (see, for example, Non-Patent Document 3). However, the acid catalyst remains in the unexposed areas even after the thermal cyclization process, which may have a serious adverse effect on the semiconductor device. Therefore, this technology is applied to the polybenzoxazole precursor system to perform the cyclization reaction. It is difficult to lower the temperature.

  Further, in the hydroxyamide group-containing polyimide precursor or hydroxyamide group-containing polyimide system obtained from the hydroxyamide group-containing tetracarboxylic dianhydride and diamine, the thermal cyclization step after pattern formation can be performed at a lower temperature. If possible, useful materials can be provided in the industrial field, but such materials are not known.

Japanese Patent Laid-Open No. 11-100503 “Journal of Applied Polymer Science”, 1994, 53, 1513-1524. “High Performance Polymer”, 2006, 18, 603-615 “Polymer Journal”, 2005, 37, 517-521

  Accordingly, an object of the present invention is to provide a hydroxyamide group-containing alicyclic polyimide or a precursor thereof having high transmittance at i-line (365 nm). Another object of the present invention is to provide a positive photosensitive resin composition comprising a diazonaphthoquinone photosensitizer in the hydroxyamide group-containing alicyclic polyimide or a precursor thereof, and the positive photosensitive resin. A polybenzoxazole imide film useful as a protective film for a semiconductor device and a plastic for flexible LCD, which is obtained by subjecting a film of the resin composition to pattern exposure and then undergoing an alkali development / washing / heat dehydration cyclization reaction process, and the polybenzo The object is to provide a method for producing a fine pattern of an oxazoleimide film.

  In view of the above problems, as a result of intensive studies, a hydroxyamide group-containing alicyclic polyimide precursor containing a repeating unit represented by the following formula (3) or a repeating unit represented by the following formula (4) A positive type photosensitive resin composition obtained by dispersing a diazonaphthoquinone photosensitizer in a hydroxyamide group-containing alicyclic polyimide contains excellent photosensitivity, and further exhibits this at 270 ° C. A film composed of polybenzoxazole imide containing a repeating unit represented by the following formula (5), which can be completely thermally cyclized at a lower temperature than the oxazole precursor system, is obtained at 250 ° C. Since it has the above high glass transition temperature, it discovered that it became a useful material as a protective film of the integrated circuit of a semiconductor element, and came to complete this invention.

  That is, the gist of the present invention is as follows.

1. The following general formula (1):
(In formula (1), A represents a tetravalent aromatic group.) A hydroxyamide group-containing alicyclic tetracarboxylic dianhydride represented by:

2. The following general formula (2):
(In formula (2), B represents a divalent aromatic group or an aliphatic group.) An imide group-containing alicyclic dicarboxylic acid represented by:

3. The following general formula (3) obtained by equimolar polyaddition reaction of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride described in the summary 1 and a diamine:

(In formula (3), A represents a tetravalent aromatic group, and B represents a divalent aromatic group or an aliphatic group.) A hydroxyamide group-containing alicyclic group containing a repeating unit represented by Polyimide precursor.

4). The following general formula (4):

(In formula (4), A represents a tetravalent aromatic group and B represents a divalent aromatic group or an aliphatic group.) A hydroxyamide group-containing alicyclic group containing a repeating unit represented by Polyimide.

5. The following general formula (5):
(In Formula (5), A represents a tetravalent aromatic group and B represents a divalent aromatic group or an aliphatic group.) The polybenzoxazole imide containing the repeating unit represented by this.

6). The hydroxyamide group-containing alicyclic polyimide according to Summary 4, wherein the hydroxyamide group-containing alicyclic polyimide precursor described in Summary 3 is subjected to an imidization reaction by heating or using a chemical imidization reagent. Manufacturing method.

7). The amide group-containing alicyclic dicarboxylic acid or derivative thereof according to summary 2 is subjected to an equimolar polycondensation reaction with bis (o-aminophenol) or a derivative thereof. Manufacturing method of alicyclic polyimide.

8). The hydroxyamide group-containing alicyclic polyimide precursor described in Summary 3 or the hydroxyamide group-containing alicyclic polyimide described in Summary 4 is subjected to a dehydration ring-closing reaction by heating or using a chemical imidization reagent. The manufacturing method of the polybenzoxazole imide of the summary 5.

9. The equimolar polycondensation cyclization reaction of the imide group-containing alicyclic dicarboxylic acid or derivative thereof according to summary 2 and bis (o-aminophenol) or derivative thereof in one step at high temperature in the presence of a condensing agent 6. A process for producing a polybenzoxazole imide according to item 5, wherein

10. A positive photosensitive resin composition comprising the hydroxyamide group-containing alicyclic polyimide precursor described in Summary 3 or the hydroxyamide group-containing alicyclic polyimide described in Summary 4 containing a diazonaphthoquinone photosensitizer.

11. The polybenzoate according to summary 5, wherein the film of the positive photosensitive resin composition described in summary 10 is subjected to pattern exposure and alkali development, and then subjected to a dehydration ring-closing reaction by heating or using a chemical imidization reagent. A method for producing a fine pattern of an oxazoleimide film.

12 A protective film for a semiconductor device comprising the polybenzoxazole imide according to the fifth aspect.

13. A plastic substrate for display comprising the polybenzoxazole imide according to the fifth aspect.

  The hydroxyamide group-containing alicyclic tetracarboxylic dianhydride of the present invention exhibits high polymerization reactivity with a diamine, and gives a hydroxyamide group-containing alicyclic polyimide precursor having a high polymerization degree and a corresponding polyimide. In addition, the photosensitive resin composition obtained by dispersing a diazonaphthoquinone photosensitizer in the hydroxyamide group-containing alicyclic polyimide precursor and the corresponding polyimide can form a high-resolution positive pattern, Furthermore, it can be heat-cured (dehydration cyclization reaction) at a lower temperature than the conventional polybenzoxazole precursor system. Furthermore, since the polybenzoxazole imide film thus obtained has a high glass transition temperature of 250 ° C. or higher, it is extremely useful as a buffer coat film for integrated circuits.

<Molecular design>
First, in order to polymerize the hydroxyamide group-containing alicyclic polyimide of the present invention containing the repeating unit represented by the above formula (4) and its precursor containing the repeating unit represented by the above formula (3). The hydroxyamide group-containing alicyclic tetracarboxylic dianhydride monomer used will be described. According to the present invention, a photosensitive material satisfying the above required characteristics can be obtained by using a hydroxyamide group-containing alicyclic tetracarboxylic dianhydride represented by the following formula (1).
(In formula (1), A represents a tetravalent aromatic group.)

  According to the present invention, the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride is obtained by using nuclear hydrogenated trimellitic acid (hereinafter H) instead of trimellitic anhydride (hereinafter referred to as TMA) or a derivative thereof. -TMA) or a derivative thereof, and can be easily produced by reacting with bis (o-aminophenol) or a derivative thereof. By using H-TMA, the intramolecular charge transfer interaction is completely prevented, and the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride is almost uncolored in contrast to the case of using TMA. be able to. By using this hydroxyamide group-containing alicyclic tetracarboxylic dianhydride, a substantially colorless and transparent hydroxyamide group-containing alicyclic polyimide and its precursor can be obtained by reaction with diamine. A characteristic of a film (film) produced using these is that it has an extremely high light transmittance in the bright line of high-pressure mercury, i.e., i-line (365 nm), which is a commonly used irradiation light source. If the light transmittance of the resin that composes the film is low, the irradiated ultraviolet rays are not efficiently absorbed by the photosensitive agent dispersed in the film, and the ultraviolet irradiation time required for pattern formation is significantly increased (decrease in sensitivity). However, the hydroxyamide group-containing alicyclic polyimide of the present invention and its precursor do not have such a problem.

Moreover, the hydroxyamide group-containing alicyclic polyimide of the present invention containing the repeating unit represented by the above formula (4) is an imide group-containing alicyclic dicarboxylic acid of the present invention represented by the following formula (2): It can also be produced by equimolar polycondensation reaction between the derivative and bis (o-aminophenol) or its derivative.
(In formula (2), B represents a divalent aromatic group or aliphatic group.)

  The imide group-containing alicyclic dicarboxylic acid can be easily produced from H-TMA and diamine. In formula (2), B is a diamine residue and represents a divalent aromatic group or an aliphatic group. Regardless of whether the diamine component used in the production of the imide group-containing alicyclic dicarboxylic acid is aliphatic or aromatic, the substantially uncolored dicarboxylic acid can be obtained. This is because even if B in the formula (2) is an aromatic group, the intramolecular charge transfer interaction is completely hindered by the imide group bonded to the cyclohexane ring. Furthermore, the hydroxyamide group-containing alicyclic polyimide of the present invention obtained by an equimolar polycondensation reaction of the imide group-containing alicyclic dicarboxylic acid or its derivative with bis (o-aminophenol) or its derivative is extremely High transparency.

  A feature of the present invention is that a hydroxyamide group-containing alicyclic polyimide precursor containing a repeating unit represented by the above formula (3) is heated in a solution under mild conditions, thereby affecting the hydroxyamide group. By performing only thermal imidization without giving (without cyclization), a hydroxyamide group-containing alicyclic polyimide containing a repeating unit represented by the above formula (4) can be produced. For example, after forming the positive pattern, the hydroxyamide group can be completely converted into a benzoxazole ring by heat treatment at a temperature higher than the imidization temperature. In this way, the phenolic OH group can be completely eliminated in the end, so that when it is applied as a protective film of a semiconductor element, unexpected serious problems caused by ion migration and water absorption are caused. It can be avoided.

  Another feature of the present invention is that thermal cyclization (oxazole ring formation) is possible at a heat treatment temperature lower than that of an ordinary polybenzoxazole precursor system. Such “cold cyclization” is performed through the bis (o-aminophenol) residue and the amide group in the hydroxyamide group-containing alicyclic polyimide of the present invention containing the repeating unit represented by the formula (4). This is based on the fact that the bonded carboxylic acid residues are not aromatic but alicyclic.

  When the hydroxyamide group-containing alicyclic polyimide of the present invention is combined with DNQ to produce a photosensitive resin composition film by a solution casting method, the hydroxyamide group-containing alicyclic polyimide is N, N-dimethylformamide (DMF). And N-methyl-2-pyrrolidone (NMP) and the like must have high solubility and varnish stability (no gelation or the like). In general, aromatic polyimide is poor in solvent solubility due to strong intermolecular force between imide groups, but the hydroxyamide group-containing alicyclic polyimide of the present invention is due to the presence of bulky nuclear hydrogenated trimellitimide groups. Intermolecular interactions between imide groups are weaker than usual, and as a result, high solvent solubility is maintained.

  Another feature of the hydroxyamide group-containing alicyclic polyimide of the present invention is that the skeleton contains an imide group in addition to the phenolic OH group, so that the solubility in an alkaline aqueous solution is appropriately controlled. It is in. Therefore, it is advantageous for forming a high-resolution positive pattern.

  The polybenzoxazole imide obtained by thermal cyclization of the hydroxyamide group-containing alicyclic polyimide of the present invention is substantially colorless and transparent, has high solution processability (thick film forming ability), and has a high glass transition temperature. Application to plastic substrates for flexible displays is possible. Since the presence of the nuclear hydrogenated trimellitimide group has an appropriate intermolecular force while maintaining solvent solubility, improvement of the gas barrier property required in the above applications is also expected.

<Method for producing hydroxyamide group-containing alicyclic tetracarboxylic dianhydride>
The manufacturing method of this hydroxyamide group containing alicyclic tetracarboxylic dianhydride is not specifically limited, A well-known method is applicable. Specifically, an amidation reaction is performed using a derivative of bis (o-aminophenol) and nuclear hydrogenated trimellitic anhydride (H-TMA) which are raw materials. As an applicable method at this time, the amino group of bis (o-aminophenol) and the carboxyl group of H-TMA are directly dehydrated at a high temperature, or an amide using a condensing agent such as triphenyl phosphite / pyridine or dicyclohexylcarbodiimide. And a method of converting a carboxyl group of H-TMA into an acid halide and reacting this with bis (o-aminophenol) in the presence of a deoxidizer (base) (acid halide method). . Among the above-mentioned methods, the acid halide method can be preferably applied in terms of economy and reactivity.

  When applying the acid halide method, nuclear hydrogenated trimellitic anhydride chloride is preferably used. When this is reacted with bis (o-aminophenol), a silylating agent can also be used in order to increase the selectivity of the reaction. That is, in order to avoid reaction (esterification reaction) with hydroxyl groups in bis (o-aminophenol), both amino groups and hydroxyl groups in bis (o-aminophenol) are silylated using a silylating agent. By doing so, the silylated hydroxyl group loses the reactivity, and the amidation reaction can be selectively performed. Usually, the amidation reaction can be substantially selectively carried out by carrying out the reaction at a low temperature such as −20 to 0 ° C. In addition, addition of a salt such as lithium chloride is one of effective methods for preferentially carrying out the amidation reaction.

  Next, a method for synthesizing the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride by the acid halide method will be specifically described, but it is not particularly limited. First, nuclear hydrogenated trimellitic acid is converted to acid anhydride, and then converted to acid chloride to synthesize nuclear hydrogenated trimellitic anhydride chloride.

  The manufacturing method of a nuclear hydrogenated trimellitic anhydride can employ | adopt a publicly known method, and is not specifically limited. As a specific example of the method for producing nuclear hydrogenated trimellitic anhydride, it can be obtained by hydrogenating trimellitic acid or trimellitic anhydride. Alternatively, the esterified product of trimellitic acid can be nucleohydrogenated, and then the ester portion can be hydrolyzed and dehydrated in the molecule to obtain an acid anhydride. Specifically, for example, it is disclosed in US Patent Application Publication No. 5412108 that it can be produced by nuclear hydrogenation of trimellitic anhydride. In the published US application, it is considered advantageous to use an Rh catalyst supported on a specific carrier as a hydrogenation catalyst that can be used for nuclear hydrogenation. In addition, any catalyst that uses a metal capable of hydrogenating aromatic nuclei such as Pd, Ru, Ni, and Pt can be used without particular limitation. These metal catalysts may be supported on a support or used alone, and further, other components may be added to these metals as required.

  When the nuclear hydrogenation reaction is carried out, usually, the three substituents on the cyclohexane ring are a mixture of four stereoisomers (eight including the optical isomers). These stereoisomers may be used in the next reaction as they are as a mixture, or may be used after increasing the concentration of a single or specific isomer by performing purification such as recrystallization. Also good. In addition, as a method for selectively obtaining a specific isomer, for example, when a method described in US Pat. No. 5,412,108 is used, a product in which all three substituents are controlled to be cis is used as a main component. Can be obtained as In this case, the purity of all cis isomers is usually 90% or more, preferably 95% or more, and more preferably 98% or more.

  After the nuclear hydrogenation reaction, some of the metal of the hydrogenation catalyst may elute, but depending on the application, it is desirable to remove the eluted metal. The eluted metal can be removed or reduced by, for example, passing through a zeta potential filter or an ion exchange resin. The amount of metal contained in the hydrogenated trimellitic acid thus obtained is usually 1000 ppm or less, preferably 100 ppm or less, more preferably 10 ppm or less.

  In the product after the nuclear hydrogenation reaction of trimellitic acid, when a part or all of the 1,2-dicarboxylic anhydride ring part is opened to become 1,2-dicarboxylic acid, heat under reduced pressure. The 1,2-dicarboxylic acid moiety may be converted to an acid anhydride ring by treatment. 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 at that time, and the upper limit is 0.1 MPa, preferably 0.05 MPa.

  As a method of converting the 1,2-dicarboxylic acid moiety into an acid anhydride ring, a method of treating with an acid anhydride of an organic acid can be employed in addition to the method of heating under reduced pressure as described above. 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. In this case, the lower limit is 30 ° C., preferably 50 ° C., and the upper limit is 200 ° C., preferably 150 ° C. The ratio of the compound having an acid anhydride ring thus obtained is usually 95 mol% or more, preferably 98 mol% or more, more preferably 99 mol in the total of the nuclear hydrogenated trimellitic acid and its acid anhydride. % Or more.

  Next, the nuclear hydrogenated trimellitic anhydride is converted to acid chloride. As the synthesis method, a usual method for synthesizing a corresponding acid chloride from a carboxylic acid can be used. Specific examples include a method using thionyl chloride, a method using oxalyl chloride, a method using phosphorus trichloride, a method using another acid chloride such as benzoic acid chloride, and the like. Of these, thionyl chloride is preferably used from the viewpoint of easiness of distilling off the excessively used chlorination reagent.

  As a method for producing nuclear hydrogenated trimellitic anhydride chloride using thionyl chloride, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2004-203792 is known. In addition, when chlorinating nuclear hydrogenated trimellitic anhydride using a chlorinating agent, a catalyst such as N, N-dimethylformamide or pyridine can be used, but the reaction is greatly hindered without using these. There is no. The obtained chlorinated product may be remarkably colored due to the presence of the catalyst. In that case, it is preferable to produce without using these catalysts.

  The amount of the chlorination reagent used is a reaction equivalent or an excess amount, but the lower limit is usually 1 mol equivalent or more, preferably 5 mol equivalent or more, more preferably 10 mol equivalent or more. On the other hand, although the upper limit is not particularly limited, an amount of 100 mole equivalent or less, preferably 50 mole equivalent or less is used from an economical viewpoint. Although the reaction can be carried out at room temperature, it is usually carried out by heating. As for the temperature employed, the lower limit is 30 ° C., preferably 50 ° C., and the upper limit is the reflux temperature of the chlorination reagent used.

  After the reaction, the excessively used chlorination reagent is removed. The removal method is not particularly limited, and distillation, extraction, and the like can be applied. In the case of distilling off by distillation, a solvent that forms an azeotropic composition with the chlorination reagent may be added and distilled off in order to increase the efficiency. For example, when distilling off thionyl chloride, benzene or toluene can be added and distilled off azeotropically. The obtained acid chlorinated product can be further purified by recrystallization using a non-polar solvent such as hexane or cyclohexane, but usually it is sufficiently pure even without such purification operation. In some cases, it can be used as it is in the next reaction step.

  In addition, as a method for producing nuclear hydrogenated trimellitic anhydride chloride, 1,2-dicarboxylic acid portion of 1,2,4-cyclohexanetricarboxylic acid obtained by hydrogenation of trimellitic acid described above is once acidified. In addition to the method in which the remaining carboxylic acid is converted to acid chloride after forming an anhydride ring, acid chlorideation and acid anhydride conversion may be performed simultaneously by directly acting a chlorinating agent on 1,2,4-cyclohexanetricarboxylic acid. it can. In that case, the above-described reaction conditions can be applied as they are except that the amount of the chlorination reagent used in the acid chloride is changed. The lower limit of the amount of the chlorinating agent used is usually 2 molar equivalents or more, preferably 5 molar equivalents or more, and more preferably 10 molar equivalents or more. On the other hand, although the upper limit is not particularly limited, an amount of 100 mole equivalent or less, preferably 50 mole equivalent or less is used from an economical viewpoint.

  When producing nuclear hydrogenated trimellitic anhydride chloride by reacting nuclear hydrogenated trimellitic anhydride or 1,2,4-cyclohexanetricarboxylic acid with a chlorinating agent, it may be carried out using a solvent. Good. The solvent which can be used in this case can be used without limitation as long as it is a solvent in which the chlorinating agent used and the product, the nuclear hydrogenated trimellitic anhydride chloride, dissolve and the chlorinating agent does not react. Examples of usable solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and acetone. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, butyl acetate and gamma butyrolactone, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Of these, toluene, heptane, and tetrahydrofuran are preferable in terms of solubility and stability. These solvents may be used alone or in combination with a plurality of arbitrary solvents. The amount of the solvent used is usually 5% by mass, preferably 10% by mass, and the upper limit of the mass concentration of the nuclear hydrogenated trimellitic anhydride or 1,2,4-cyclohexanetricarboxylic acid as the substrate. 50% by mass, preferably 40% by mass.

  The purity of the nuclear hydrogenated trimellitic anhydride chloride obtained by performing purification as necessary in this manner is usually 90% or more, preferably 95% or more, and more preferably 98% or more. Major impurities include diacid chlorides and triacid chlorides (including stereoisomers) produced by acid chloride conversion of multiple carboxyl groups of tricarboxylic acid with an acid anhydride ring opened, and dimethylformamide as a catalyst. Is used, there is a decomposition product thereof, a dimethylamide form of nuclear hydrogenated trimellitic acid, etc., but these are preferably present in a small amount, usually 5% by mass or less, more preferably 3% by mass or less. More preferably, it is 1 mass% or less.

  Next, the method for producing the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride of the present invention using the nuclear hydrogenated trimellitic anhydride chloride and bis (o-aminophenol) obtained as described above. Is described in detail, but is not limited thereto. First, nuclear hydrogenated trimellitic anhydride chloride (Amol) is dissolved in a solvent and sealed with a septum cap. This solution is slowly added dropwise to a solution of bis (o-aminophenol) (0.5 × Amol) and an appropriate amount of a deoxidizing agent dissolved in the same solvent using a syringe or a dropping funnel. After completion of the dropwise addition, the reaction mixture is stirred for 1 to 24 hours. When the target compound is highly soluble in the solvent used in the synthesis, first the hydrochloride formed is filtered off from the reaction mixture, the filtrate is evaporated using an evaporator, and dried in a vacuum at 20-100 ° C. for 24 hours to obtain a powder. A crude product is obtained. If the solubility of the target product is low, the target product is filtered off. When pyridine is used as the deoxidizer, it precipitates as a mixture with pyridine hydrochloride, and is washed with a large amount of water to dissolve and remove only the hydrochloride. Next, the crude product partially hydrolyzed in the partial washing step is vacuum-dried at 20 to 100 ° C. The crude product thus obtained is recrystallized with an appropriate solvent, washed, and subjected to vacuum drying to obtain a highly pure hydroxyamide group-containing alicyclic tetracarboxylic dianhydride. It is done.

  The bis (o-aminophenol) used in this reaction is not particularly limited and can be selected according to the purpose. Usable (o-aminophenol) is 3,3′-diamino-4,4′-dihydroxybiphenylsulfone, 4,4′-diamino-3,3′-dihydroxybiphenylsulfone, 3,3′-diamino. -4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenylmethane, 4,4 ′ -Diamino-3,3'-dihydroxybiphenylmethane, 2,2-bis (3-amino-4 Hydroxyphenyl) - propane as an example.

  In this reaction, usable solvent is not particularly limited, but acetone, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, N-methyl. -2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N, N-dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethyl sulfoxide (DMSO), aprotic solvents such as γ-butyrolactone (GBL), 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, and phenol, o-cresol, m- Cresol, p-cresol, o-chloroph Examples include protic solvents such as enol, m-chlorophenol, and p-chlorophenol. These solvents may be used alone or in combination of two or more. Acetone, tetrahydrofuran and 1,4-dioxane are preferably used from the viewpoint of solubility of the reaction reagent and easiness of distillation.

  Such an amidation reaction is carried out at -20 to 30 ° C, but it is desirable to carry out the reaction while cooling at -20 to 0 ° C from the viewpoint of enhancing the reaction selectivity and suppressing by-products. When the reaction temperature is higher than 30 ° C., side reactions such as esterification partially occur and the yield may be lowered, which is not preferable.

  The reaction for obtaining the hydroxyamide group-containing tetracarboxylic dianhydride is carried out in a solute concentration range of 5 to 50% by mass. In consideration of solubility of raw materials, side reaction control, and filtration step of precipitation, it is preferably performed in the range of 10 to 40% by mass.

  Although it does not specifically limit as a deoxidizer used for reaction, Inorganic bases, such as epoxy compounds, such as a propylene oxide, organic tertiary amines, such as a pyridine, a triethylamine, N, N- dimethylaniline, potassium carbonate, and sodium hydroxide. Used. Propylene oxide is preferably used from the viewpoint that the reaction does not produce hydrochloride and simplifies the isolation process.

  The precipitate produced by the reaction contains water-soluble pyridine hydrochloride when pyridine is used as a deoxidizing agent. For example, when tetrahydrofuran is used as a solvent, since pyridine hydrochloride is hardly dissolved in the solvent, the hydrochloride can be separated almost completely only by filtering the reaction solution. Usually, when the solubility of the target product is high, the target product is dissolved in the filtrate, so that the target product with high yield and sufficiently high purity can be obtained simply by distilling off the solvent from the filtrate and recrystallization from an appropriate solvent. can get.

  Generally used tetracarboxylic dianhydride is treated with an organic acid anhydride such as acetic anhydride before use in polymerization, or heated and vacuum dried to absorb moisture in the air and slightly hydrolyze. Thus, a pretreatment for completely dehydrating the ring-opened portion is often performed. However, in the case of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride according to the present invention, if it is treated with acetic anhydride, the hydroxyl group may be acetylated depending on the reaction conditions. Further, when heated at a high temperature, there is a risk that undesirable side reactions such as an intermolecular esterification reaction between a hydroxyl group and an acid anhydride group may occur in addition to a cyclization reaction of a hydroxyamide group to a benzoxazole ring. It should not be heat treated above ℃.

<Method for Producing Imido Group-Containing Alicyclic Dicarboxylic Acid>
Next, although the manufacturing method of the imide group containing dicarboxylic acid of this invention represented by the said Formula (2) is demonstrated, it is not limited to this. First, H-TMA powder (A × 2 mol) is added to a solution obtained by dissolving diamine Amol in a solvent and stirred at room temperature for 1 to 24 hours. At this stage, the acid anhydride group in H-TMA reacts with the amino group in diamine to produce a dicarboxylic acid containing an amic acid group. The amide group-containing dicarboxylic acid of the present invention is obtained by ring-closing reaction (imidization) of this amic acid group. The reaction mixture can be imidized by heating to reflux at 130 to 200 ° C, preferably 150 to 180 ° C for 30 minutes to 5 hours. Moreover, the method of adding a chemical imidation reagent in the said reaction solution is also applicable.

  Examples of the chemical imidization reagent used for imidization include a combination of an organic acid anhydride typified by acetic anhydride and a base catalyst such as pyridine. This chemical imidation reagent is added to the above-mentioned solution of the amidic acid group-containing dicarboxylic acid, and can be easily converted to the desired imide group-containing dicarboxylic acid by stirring at room temperature to 50 ° C. for 1 to 24 hours.

  The diamine that can be used in the above reaction is not particularly limited, and examples thereof include aromatic diamines and aliphatic diamines. Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4 ′. -Diaminodiphenylmethane, 4,4'-methylenebis (2-methylaniline), 4,4'-methylenebis (2-ethylaniline), 4,4'-methylenebis (2,6-dimethylaniline), 4,4'- Methylenebis (2,6-diethylaniline), 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone 3,3′-diaminodiphenylsulfone, 4,4′-diaminoben Phenone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzanilide, benzidine, 3,3′-dihydroxybenzidine, 3,3′-dimethoxybenzidine, o-tolidine, m-tolidine, 2,2′- Bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) 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, , 2- bis (4-aminophenyl) hexafluoropropane, p- terphenyl-phenylenediamine, and the like. Two or more of these aromatic diamines can be used in combination. Examples of the aliphatic diamine include a chain aliphatic diamine and a cyclic aliphatic diamine. Examples of the cyclic aliphatic diamine include 4,4′-methylenebis (cyclohexylamine), isophoronediamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-cyclohexanebis (methyl). Amine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) Examples include tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, and the like. . Two or more of these cyclic aliphatic diamines can be used in combination. Examples of chain aliphatic diamines include 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine and the like can be mentioned. Two or more of these chain aliphatic diamines can be used in combination.

  The solvent that can be used in the above reaction is not particularly limited as long as it dissolves the raw material diamine and H-TMA, but acetone, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, Dichloromethane, chloroform, 1,2-dichloroethane, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, dimethylsulfoxide, γ- Aprotic solvents such as butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, and phenol, o-cresol, m-cresol, p-cresol , O-chlorophenol, m-chloro Protic solvents such as phenol and p-chlorophenol are exemplified. These solvents may be used alone or in combination of two or more. In the case of performing imidization by heating under reflux, a solvent having a high boiling point, for example, N, N-dimethylformamide (DMF), DMAc, NMP, m-cresol, hexamethylphosphoramide, dimethylsulfoxide and the like are preferably used.

  The imide group-containing alicyclic dicarboxylic acid obtained as described above can be used for the polycondensation reaction with bis (o-aminophenol) as it is, but can be recrystallized from an appropriate solvent. Further, it can be highly purified.

<Method for producing hydroxyamide group-containing alicyclic polyimide precursor>
The method for producing the hydroxyamide group-containing alicyclic polyimide precursor of the present invention is not particularly limited, and a known method can be applied. Specifically, it is manufactured by the following method. First, a diamine composed of one component or multiple components is dissolved in a dehydrated polymerization solvent, and the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride of the present invention is used alone or as a copolymerization component with other tetramers. Combined with carboxylic dianhydride, gradually add as powder and stir using a mechanical stirrer. At this time, the total amount of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride and the total amount of diamine are charged in substantially equimolar amounts. When the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride powder is added, the hydroxyamide group-containing alicyclic carboxylic dianhydride powder is mixed in advance and then added to the solution. It can be added.

  Hereinafter, preferred specific examples will be described. First, diamine is dissolved in a polymerization solvent, and the above hydroxyamide group-containing alicyclic tetracarboxylic dianhydride is used alone or as a copolymerization component with another hydroxyamide group-containing alicyclic tetracarboxylic dianhydride. In addition, the powder is gradually added as a powder and stirred at 0 to 100 ° C., preferably 5 to 60 ° C. for 0.5 to 100 hours, preferably 1 to 50 hours using a mechanical stirrer. Under the present circumstances, the total monomer density | concentration in a solution is 1-50 mass%, Preferably it is 5-30 mass%. By carrying out the polymerization in this monomer concentration range, a uniform and high polymerization degree hydroxyamide group-containing alicyclic polyimide precursor solution can be obtained.

  Film forming properties of the above-mentioned hydroxyamide group-containing alicyclic polyimide precursor and hydroxyamide group-containing alicyclic polyimide, adhesion to the substrate, and film toughness of polybenzoxazole imide which is a thermosetting (cyclized) product thereof From the viewpoint, it is desirable that the degree of polymerization of the hydroxyamide group-containing alicyclic polyimide precursor is as high as possible. However, if the intrinsic viscosity value qualitatively representing the molecular weight is 0.2 dL / g or more, film formation There is no problem in the properties, adhesiveness and film toughness. If the intrinsic viscosity value is lower than this value, the film-forming property and film toughness are drastically lowered, which may cause a serious problem that cannot be applied to the industrial field. When polymerization is performed at a concentration lower than the above monomer concentration range, the degree of polymerization of the hydroxyamide group-containing alicyclic polyimide precursor is not sufficiently high, and the hydroxyamide group-containing alicyclic polyimide and the polybenzoxazole imide film are fragile. This is not preferable. On the other hand, when the polymerization is carried out at a concentration higher than this range, the monomer and the polymer to be produced are not sufficiently dissolved, and the polymerization may not proceed uniformly.

  In the present invention, the content of the hydroxyamide group-containing tetracarboxylic dianhydride in all the tetracarboxylic dianhydrides used for polymerization is in the range of 5 to 100 mol% from the viewpoint of positive pattern formation, The range of 30-100 mol% is preferable, and the range of 50-100 mol% is still more preferable. If it is less than 5 mol%, the dissolution rate in an alkaline aqueous solution, particularly tetramethylammonium hydroxide (TMAH) aqueous solution will be significantly reduced, or the difference in solubility between the exposed and unexposed areas will become uncontrollable, resulting in a clear fine pattern. This is not preferable because it may be difficult to form.

  In the range where the reactivity when polymerizing the hydroxyamide group-containing alicyclic polyimide precursor, the solvent solubility of the hydroxyamide group-containing alicyclic polyimide, the film forming property and the required characteristics of the polybenzoxazole imide film are not impaired, The tetracarboxylic dianhydride that can be partially used other than the hydroxyamide group-containing alicyclic 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′-biphenylsulfonetetracarboxylic dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid Water, 2,2′-bis (3,4-dicarboxyphenyl) propanoic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic dianhydride, hydroquinone-bis (trimellitic anhydride), cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc. Is mentioned. These may be used alone or in combination of two or more as copolymerization components.

  Reactivity when polymerizing the hydroxyamide group-containing alicyclic polyimide precursor according to the present invention, solvent solubility of the hydroxyamide group-containing alicyclic polyimide, film forming properties, and required characteristics of the polybenzoxazole imide film are not impaired. Although it does not specifically limit as aromatic diamine which can be used in the range, For example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2 , 4-diaminodurene, 4,4′-diaminodiphenylmethane, 4,4′-methylenebis (2-methylaniline), 4,4′-methylenebis (2-ethylaniline), 4,4′-methylenebis (2,6 -Dimethylaniline), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-diaminodi Phenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzanilide, benzidine, 3,3′-dihydroxybenzidine, 3,3′-dimethoxybenzidine, o-tolidine, m-tolidine, 2,2 ′ -Bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) 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- Examples include aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, and p-terphenylenediamine. Two or more of these may be used in combination.

  Reactivity when polymerizing the hydroxyamide group-containing alicyclic polyimide precursor according to the present invention, solvent solubility of the hydroxyamide group-containing alicyclic polyimide, film forming properties, and required characteristics of the polybenzoxazole imide film are not impaired. Although it does not specifically limit as cyclic aliphatic diamine which can be used in the range, For example, 4,4'- methylenebis (cyclohexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-1,4-diamino Cyclohexane, 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-diaminoadamada Tan, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, and the like. Two or more of these may be used in combination. On the other hand, the reactivity when polymerizing the hydroxyamide group-containing alicyclic polyimide precursor according to the present invention, the solvent solubility of the hydroxyamide group-containing alicyclic polyimide, the film forming property, and the required characteristics of the polybenzoxazole imide film Although it does not specifically limit as chain | strand-shaped aliphatic diamine which can be used in the range which does not impair, For example, 1, 3- propane diamine, 1, 4- tetramethylene diamine, 1, 5- pentamethylene diamine, 1, 6-, Hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine and the like can be mentioned. Two or more of these may be used in combination.

  The polymerization solvent that can be used is not particularly limited, but amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, cyclic ester solvents such as γ-caprolactone, ε-caprolactone, α-methyl-γ-ptyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3- Phenol solvents such as chlorophenol and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like 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 solvents, etc. Can also be used.

  The hydroxyamide group-containing alicyclic polyimide precursor of the present invention comprises a cast film obtained by coating or drying a polymerization solution (varnish) as it is or appropriately diluted on a substrate, and a photosensitive agent in the varnish. In addition to the usage form as a photosensitive resin composition film obtained by adding and dissolving and casting to form a film, after appropriately diluting the varnish, dripping, filtering and drying in a large amount of poor solvent such as water or methanol It can also be isolated as a powder.

  In the film of the hydroxyamide group-containing polyimide precursor of the present invention, in addition to the photosensitive agent, if necessary, an oxidation stabilizer, a filler, a silane coupling agent, an adhesion promoter, a wet heat stabilizer, a photopolymerization initiator, Additives such as a sensitizer, a terminal blocking agent, a crosslinking agent, a flame retardant and the like can be added.

<Method for producing hydroxyamide group-containing alicyclic polyimide>
The hydroxyamide group-containing alicyclic polyimide of the present invention is obtained by converting a hydroxyamide group-containing alicyclic polyimide precursor containing a repeating unit represented by the above formula (3) obtained by the above method into a hydroxyamide group. It can be produced by carrying out only the imidization reaction without affecting (while remaining). This is because the temperature range required for the thermal cyclization reaction from the hydroxyamide group to the benzoxazole ring is sufficiently higher (100 ° C. or higher) than the imidization reaction.

  The use form of the hydroxyamide group-containing alicyclic polyimide of the present invention includes a photosensitive resin composition film in which a solution (varnish), a cast film, a photosensitizer and the like are blended, and after appropriately diluting the varnish, It is a powder obtained by dropping, filtering and drying in a poor solvent such as methanol.

  First, the manufacturing method of the varnish and powder of a hydroxyamide group containing alicyclic polyimide is demonstrated. The hydroxyamide group-containing alicyclic polyimide precursor varnish obtained by the polymerization reaction is left as it is or after being appropriately diluted with a solvent, and then heated and refluxed in a nitrogen atmosphere to thereby produce the hydroxyamide of the present invention. A group-containing alicyclic polyimide varnish can be easily obtained. The reflux temperature at this time is 120 to 220 ° C., and the reflux time is 10 minutes to 12 hours, more preferably 150 to 190 ° C. for 1 to 5 hours. At this time, if the reflux temperature is lower than 120 ° C., it takes a very long time to complete imidization, so it is not adopted in terms of productivity. On the other hand, if it exceeds 220 ° C., not only imidation but also the remaining hydroxyamide group starts to cyclize, and the product is more likely to be colored, which is not preferable. It is also possible to control the reflux temperature and time to appropriately cyclize the hydroxyamide group and control the content of the phenolic OH group. To azeotropically distill off water, which is a by-product of the imidization reaction, toluene, xylene or the like may be added. Further, a base such as γ-picoline can be added as a catalyst.

  Since the hydroxyamide group-containing alicyclic polyimide of the present invention has extremely high solubility in various polymerization solvents usually used for polymerization of the hydroxyamide group-containing alicyclic polyimide precursor, the thermal imidization reaction There is no precipitation later, and a uniform varnish is obtained.

  From the viewpoint of film-forming property of the above-mentioned hydroxyamide group-containing alicyclic polyimide and adhesion to the substrate, and film toughness of polybenzoxazolimide which is a thermosetting (cyclized) product thereof, the hydroxyamide group-containing alicyclic type The degree of polymerization of the polyimide is preferably as high as possible, but if the intrinsic viscosity value is 0.2 dL / g or more, there is no problem in film forming property, adhesiveness, and film toughness. If the intrinsic viscosity value is lower than this value, the film-forming property and film toughness are drastically lowered, which may cause a serious problem that cannot be applied to the industrial field.

  After imidization in the solution, the varnish obtained as described above is dropped, filtered and dried in a large amount of poor solvent such as water or methanol for the purpose of removing additives, by-products and solvents. The hydroxyamide group-containing alicyclic polyimide can also be isolated as a powder. Moreover, this powder can be redissolved in the above-mentioned various solvents to obtain a varnish again.

  In addition, the imidization reaction may be carried out with acetic anhydride in combination with a tertiary amine catalyst such as pyridine or triethylamine in the varnish of the hydroxyamide group-containing alicyclic polyimide precursor instead of heat treatment exceeding 100 ° C. It is also possible to carry out by adding a chemical imidation reagent of organic anhydride such as from room temperature to 100 ° C. for 10 minutes to 24 hours. At this time, the imidation rate can also be controlled by adjusting the reaction conditions such as the amount of the chemical imidizing reagent added. However, depending on the reaction conditions, the hydroxyl group in the hydroxyamide group-containing alicyclic polyimide precursor reacts with acetic anhydride and is acetylated. Therefore, if you want to avoid acetylation, thermal imidation is better than chemical imidization. Although it is preferably adopted, when the purpose is to acetylate the hydroxyl group partially or completely, the acetylation rate can be controlled by adjusting the reaction conditions such as the amount of chemical imidization reagent added. It is.

  The hydroxyamide group-containing alicyclic polyimide of the present invention is obtained by reacting an acid dianhydride component containing the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride of the present invention with a diamine component at a high temperature in a solvent (one-pot polymerization). ), The hydroxyamide group-containing alicyclic polyimide precursor can be polymerized in one step without isolation. The polymerization reaction temperature is 120 to 220 ° C., and the reflux time is 10 minutes to 12 hours, more preferably 150 to 190 ° C. for 1 to 5 hours. At this time, if the polymerization temperature is lower than 120 ° C., it takes a very long time to complete the polymerization, and thus it is not adopted in terms of productivity. On the other hand, if it exceeds 220 ° C., not only polymerization but also the hydroxyamide group to be left begins to cyclize, and the product tends to be colored, which is not preferable. It is also possible to control the polymerization temperature and time to appropriately cyclize the hydroxyamide group and control the content of the phenolic OH group. To azeotropically distill off water, which is a by-product during the polymerization reaction, toluene, xylene or the like may be added. Further, a base such as γ-picoline can be added as a catalyst.

  Solvents that can be used for one-pot polymerization are not particularly limited, but suitable examples include aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Examples thereof include phenol solvents such as m-cresol and amide solvents such as NMP. After the one-pot polymerization, the resulting varnish can be dropped and filtered into a large amount of poor solvent such as water or methanol to isolate the polyimide as a powder. The powder can be redissolved in various solvents to form a varnish.

  In addition to producing the hydroxyamide group-containing alicyclic polyimide of the present invention as described above, the imide group-containing alicyclic dicarboxylic acid and bis (o-aminophenol) of the present invention can be produced as monomer raw materials. . The polymerization method will be specifically described below, but is not particularly limited.

  When the hydroxyamide group-containing alicyclic polyimide of the present invention is polymerized from the imide group-containing alicyclic dicarboxylic acid and bis (o-aminophenol) of the present invention, at least the dicarboxylic acid component is activated and converted to active acyl. It is necessary to keep. As the method, 1-hydroxybenzotriazole and a carboxyl group in dicarboxylic acid are reacted in advance to activate as a diester, a method of converting the dicarboxylic acid into an acid halide, and in a reaction solution in the presence of a condensing agent. An example is a method of activating a carboxyl group. Among these, the acid halide method has the highest activity of the dicarboxylic acid and tends to give a higher polymer. From this viewpoint, the polycondensation reaction by the acid halide method will be described below.

  As a method for converting the imide group-containing alicyclic dicarboxylic acid of the present invention into an acid halide, for example, acid chloride, the method used when acidifying the above nuclear hydrogenated trimellitic anhydride may be applied as it is. it can. That is, the acid chloride can be easily formed using thionyl chloride in the presence of a catalyst such as N, N-dimethylformamide.

  If the imide group-containing alicyclic dicarboxylic acid is converted to an acid chloride, an equimolar polycondensation reaction with bis (o-aminophenol) can be carried out. However, acid chloride and bis (o-aminophenol) For the purpose of enhancing the selectivity of the reaction with the amino group therein, the following pretreatment can be performed. First, a silylating agent such as trimethylsilyl chloride is dropped into bis (o-aminophenol) dissolved in a polymerization solvent in the presence of an acid acceptor such as pyridine to silylate both the amino group and the hydroxyl group. This makes the amino group highly reactive while the nucleophilicity of the hydroxyl group disappears. Thereby, the high polymer of the hydroxyamide group containing alicyclic polyimide of this invention can be obtained easily.

  The hydroxyamide group-containing alicyclic polyimide is polymerized by the following procedure. In the presence of a hydrogen chloride scavenger such as pyridine and an inorganic salt such as lithium chloride, an equimolar amount of the imide group-containing alicyclic dicarboxylic acid chloride is added to the silylated bis (o-aminophenol) solution. Gradually add so that does not rise. After stirring for 24 hours at room temperature, a viscous and homogeneous polymerization solution is obtained.

  Although it does not specifically limit as a bis (o-aminophenol) component which can be used in the said polycondensation reaction, 3,3'-diamino-4,4'-dihydroxybiphenyl sulfone, 4,4'-diamino-3 , 3′-dihydroxybiphenylsulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 2,2-bis (3-amino-4- Hydroxyphenyl) hexafluoropropane, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino -4,4'-dihydroxybiphenylmethane, 4,4'-diamino-3,3'-dihydroxy Biphenyl methane, 2,2-bis (3-amino-4-hydroxyphenyl) - propane as an example. These may be used alone or in combination of two or more.

  As a usable polymerization solvent, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, γ-butyrolactone and a mixed solvent thereof are used. Examples of polymerization solvents that can be used other than the solvents described above include N, N-diethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2- Aprotic solvents such as (methoxyethyl) ether, terahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, phenol, o-cresol, Examples include protic solvents such as m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol. These solvents may be used alone or in combination of two or more.

  Moreover, as a dicarboxylic acid component that can be partially used in addition to the imide group-containing alicyclic dicarboxylic acid of the present invention, the polymerization reactivity and required characteristics of the hydroxyamide group-containing alicyclic polyimide of the present invention are not significantly impaired. Terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid Acid, 4,4′-diphenylsulfone dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1, -Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-anthracene Dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples include acids and 1,4-cyclohexanedicarboxylic acid. Two or more of these may be used in combination.

  By appropriately diluting a high viscosity solution of a silylated hydroxyamide group-containing alicyclic polyimide obtained from a tetrasilylated bis (o-aminophenol) and a dicarboxylic acid dichloride, and precipitating and washing in a large amount of water, Silylated hydroxyamide group-containing alicyclic polyimides can be isolated. Moreover, it can be easily desilylated by precipitation using aqueous hydrochloric acid or methanol instead of water, and the hydroxyamide group-containing alicyclic polyimide of the present invention can be isolated as a powder.

  Next, the manufacturing method of the film of a hydroxyamide group containing alicyclic polyimide is demonstrated. The hydroxyamide group-containing alicyclic polyimide precursor varnish is cast on a substrate such as an insoluble polyimide film, glass, copper, aluminum, stainless steel or silicon, and is heated at 40 to 180 ° C, preferably 50 to 150 ° C in an oven. dry. The obtained hydroxyamide group-containing alicyclic polyimide precursor film is heated on a substrate in a vacuum, in an inert gas such as nitrogen, or in air at 180 to 300 ° C., preferably 200 to 280 ° C. Thereby, the film of the hydroxyamide group-containing alicyclic polyimide of the present invention can be produced. As a heating condition at this time, a temperature of 180 ° C. or higher is employed from the viewpoint of sufficiently performing the imidization ring-closing reaction, and a temperature of 300 ° C. or lower is employed from the viewpoint of suppressing cyclization of the hydroxyamide group. The imidization is preferably performed in vacuum or in an inert gas, but may be performed in air if the imidization temperature is not too high.

  The hydroxyamide group-containing alicyclic polyimide varnish can be cast and dried on the substrate to produce a hydroxyamide group-containing alicyclic polyimide film. At this time, the drying temperature is not particularly limited as long as the solvent is completely evaporated and removed, and is dried at 40 to 300 ° C., preferably 100 to 280 ° C.

  In the hydroxyamide group-containing alicyclic polyimide film of the present invention, in addition to the photosensitive agent, an oxidation stabilizer, a filler, a silane coupling agent, an adhesion promoter, a wet heat stabilizer, a photopolymerization initiator, if necessary. Additives such as a sensitizer, a terminal blocking agent, a crosslinking agent, a flame retardant and the like can be added.

<Method for producing polybenzoxazole imide>
Next, the manufacturing method of the polybenzoxazole imide of this invention containing the repeating unit represented by the said Formula (5) is demonstrated. The usage form is a photosensitive resin composition film containing a varnish, a cast film, a photosensitive agent, etc., and after appropriately diluting the varnish, dripping, filtering, and filtering into a large amount of poor solvent such as water or methanol. It is a powder obtained by drying.

  First, the manufacturing method of the said polybenzoxazole imide film is demonstrated. One method is a method using the hydroxyamide group-containing alicyclic polyimide precursor of the present invention. That is, the varnish of the hydroxyamide group-containing alicyclic polyimide precursor is cast on, for example, an insoluble polyimide film, glass, copper, aluminum, stainless steel, silicon or the like, and is heated in an oven at 40 to 180 ° C., preferably Dry at 50-150 ° C. The resulting film of the hydroxyamide group-containing alicyclic polyimide precursor is heated on a substrate in vacuum, in an inert gas such as nitrogen, or in air at 250 to 400 ° C., preferably 270 to 350 ° C. Thus, imidization and benzoxazolation both occur, and the polybenzoxazole imide film of the present invention can be produced. This thermal curing (cyclization) step is desirably performed in a vacuum or in an inert gas, but may be performed in air if the treatment temperature is not too high.

  Another method is a method using the hydroxyamide group-containing alicyclic polyimide of the present invention. That is, a hydroxyamide group-containing alicyclic polyimide varnish is cast on, for example, the above substrate and dried in an oven at 40 to 180 ° C, preferably 50 to 150 ° C. The resulting hydroxyamide group-containing alicyclic polyimide film is heated on a substrate in a vacuum, in an inert gas such as nitrogen, or in air at 250 to 400 ° C., preferably 270 to 350 ° C. The amide group is completely converted to a benzoxazole ring, and a polybenzoxazole imide film is obtained. This thermosetting (cyclization) step is desirably performed in vacuum or in an inert gas, but may be performed in air if the treatment temperature is not too high.

  The polybenzoxazole imide of the present invention can also be obtained by heating and refluxing the hydroxyamide group-containing alicyclic polyimide and its precursor varnish at 180 to 250 ° C. At that time, when the polybenzoxazole imide is soluble in the solvent, it is obtained as a uniform varnish, and when it is insoluble, it is obtained as a precipitate. When a uniform varnish of polybenzoxazole imide is obtained, a polybenzoxazole imide film can be produced by casting and drying the varnish on the substrate. At this time, the drying temperature is not particularly limited as long as the solvent is completely evaporated and removed, and is dried at 40 to 400 ° C., preferably 100 to 350 ° C.

  The polybenzoxazole imide of the present invention is an equimolar polycondensation reaction between the imide group-containing alicyclic dicarboxylic acid of the present invention represented by the above formula (2) and bis (o-aminophenol) in the presence of a condensing agent ( It can also be produced by one-pot polymerization). Although the polymerization method is demonstrated below, it is not limited to this.

  An imide group-containing alicyclic dicarboxylic acid of the present invention and an equimolar amount of bis (o-aminophenol) are placed in a reaction vessel, and a polymerization solvent is added. While stirring with a stirrer, the temperature is raised stepwise from 100 ° C. to 10 ° C. in a nitrogen atmosphere (holding at each temperature for 10 minutes), and finally held at 200 to 230 ° C. for 10 minutes to 2 hours. After cooling to room temperature, it is precipitated in water, washed with a large amount of water until the washing water becomes neutral, then further washed with methanol, and finally vacuum dried at 100 ° C. to form a white precipitate of the polybenzoxazole. obtain.

  The monomer concentration at the time of polymerization is 5 to 30% by mass, preferably 7 to 20% by mass. When the monomer concentration is less than 5% by mass, the degree of polymerization of the polybenzoxazole imide may not be sufficiently high, and when it exceeds 30% by mass, the monomer may not be sufficiently dissolved and a uniform solution may not be obtained.

  The polymerization solvent and condensing agent that can be used are not particularly limited, but polyphosphoric acid or phosphorus pentoxide-methanesulfonic acid is used as the polymerization solvent that also serves as the condensing agent, and polyphosphoric acid is particularly preferably used.

  The polymerization reaction is preferably performed by gradually increasing the temperature as described above, and should not be rapidly increased to 200 ° C. Otherwise, the alicyclic structure in the imide group-containing alicyclic dicarboxylic acid of the present invention is partially decomposed, and the finally obtained polybenzoxazole may be remarkably colored, and the degree of polymerization may not be sufficiently high. The polymerization temperature is preferably raised to at least 200 ° C. When the polymerization reaction is performed at a temperature lower than 200 ° C., the degree of polymerization may not be sufficiently high.

  Although it does not specifically limit as a bis (o-aminophenol) component which can be used in the said polycondensation reaction, 3,3'-diamino-4,4'-dihydroxybiphenyl sulfone, 4,4'-diamino-3 , 3′-dihydroxybiphenylsulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 2,2-bis (3-amino-4- Hydroxyphenyl) hexafluoropropane, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino -4,4'-dihydroxybiphenylmethane, 4,4'-diamino-3,3'-dihydroxy Biphenyl methane, 2,2-bis (3-amino-4-hydroxyphenyl) - propane as an example. These may be used alone or in combination of two or more.

  Further, dicarboxylic acids that can be partially used within a range that does not significantly impair the polymerization reactivity and required properties of the polybenzoxazole imide according to the present invention include terephthalic acid, isophthalic acid, phthalic acid, and 2,5-dimethyl. Terephthalic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid 4,4′-biphenyldicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 1,2 -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarbo Acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-anthracenedicarboxylic acid, oxalic acid, malonic acid, succinic acid Examples include glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, 1,2-cyclohexanedicarboxylic acid, and the like. Two or more of these may be used in combination.

  In the polybenzoxazole imide of the present invention, which is polymerized in one step from imide group-containing alicyclic dicarboxylic acid and bis (o-aminophenol) in polyphosphoric acid, since it does not go through the precursor, high temperature dehydration as described above There is no need for a cyclization reaction step and there is no concern that the resulting polybenzoxazole imide film will be colored. In addition, this one-step polymerization step includes activation of the dicarboxylic acid component necessary for polymerization of the hydroxyamide group-containing polyimide of the present invention corresponding to the precursor of the polybenzoxazole imide and silylation of bis (o-aminophenol). Such a complicated process is not included.

  Since the polybenzoxazole imide of the present invention has a bulky nuclear hydrogenated trimellitimide group in the skeleton, it exhibits high solubility in an organic solvent. The polybenzoxazolimide varnish is cast on a substrate such as an insoluble polyimide film, silicon, copper, aluminum, glass, etc., and dried in a hot air dryer at 50 to 150 ° C. for 10 minutes to several hours, and further 100 to By heat-treating at 350 ° C., preferably 150 ° C. to 300 ° C., a transparent and tough polybenzoxazole imide film can be produced. In the heat treatment at a temperature exceeding 350 ° C., the polybenzoxazole film may be markedly colored. In order to suppress coloration of the film, it is desirable to perform the heat treatment in a vacuum or in an inert gas atmosphere such as nitrogen, but no serious problem arises even in air unless the temperature is too high.

  The organic solvent used when the polybenzoxazole imide is used as a varnish is not particularly limited, but usable solvents include N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoramide, N- Methyl-2-pyrrolidone, γ-butyrolactone and a mixed solvent thereof are used. Polymerization solvents that can be used other than the above solvents include N, N-diethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2- Aprotic solvents such as (methoxyethyl) ether, terahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, phenol, o-cresol, Examples include protic solvents such as m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol. These solvents may be used alone or in combination of two or more.

  In order to apply the polybenzoxazole imide obtained as described above as a protective film of a semiconductor element, for example, a buffer coat film or an interlayer insulating film of a semiconductor integrated circuit, and a plastic substrate for display, a heat resistance index The glass transition temperature is preferably 200 ° C. or higher, and more preferably 230 ° C. or higher. If the temperature is lower than 200 ° C., serious problems such as film deformation, foaming, and poor adhesion may occur in the thermal process during mounting. In addition, as a measure of film toughness, there is no major problem unless breakage is observed in the 180 ° bending simple test. Further, the elongation at break in the tensile test is preferably 5% or more, and preferably 10% or more. More preferred.

  In the polybenzoxazole imide film of the present invention, additives such as an oxidation stabilizer, a filler, a silane coupling agent, an adhesion promoter, a wet heat stabilizer, a cross-linking agent, a terminal sealing agent, a flame retardant, etc. are added as necessary. Can be added.

<Method for producing positive photosensitive resin composition>
Next, although the manufacturing method of the positive photosensitive resin composition which concerns on this invention is demonstrated, it is not limited to this. A positive photosensitive resin composition can be produced by adding and dissolving a diazonaphthoquinone (DNQ) photosensitizer to the hydroxyamide group-containing alicyclic polyimide of the present invention or its precursor varnish. A positive photosensitive resin composition film can be obtained by applying a positive photosensitive resin composition on a substrate and drying it with warm air at 40 to 120 ° C., preferably 60 to 100 ° C. for 1 minute to 3 hours. . The film thickness of the positive photosensitive resin composition film is preferably in the range of 0.1 to 20 μm.

  The hydroxyamide group-containing alicyclic polyimide or precursor thereof of the present invention is characterized in that alkali solubility is appropriately controlled. When the diazonaphthoquinone photosensitizer is not dispersed, it is alkali-soluble, but when it contains a DNQ photosensitizer having a dissolution inhibiting action, it becomes alkali-insoluble. When this photosensitive resin composition film is irradiated with ultraviolet rays through a photomask, the DNQ photosensitizer in the exposed area is changed to alkali-soluble indenecarboxylic acid by a photoreaction, so that only the exposed area is soluble in an alkaline aqueous solution. Become. As a result, a positive pattern can be formed.

  Examples of the DNQ photosensitizer include 1,2-naphthoquinone-2-diazide-5-sulfonic acid and low molecular hydroxy compounds of 1,2-naphthoquinone-2-diazide-4-sulfonic acid, such as 2,3,4- Examples include trihydroxybenzophenone, 1,3,5-trihydroxybenzene, 2- and 4-methyl-phenol, esters of 4,4′-hydroxy-propane, and the like.

  When the mixing ratio of the DNQ photosensitizer dispersed in the positive photosensitive resin composition film is too small, the difference in solubility between the exposed area and the unexposed area is too small, and pattern formation cannot be performed by development. If it is too high, the film properties (glass transition temperature, film toughness, thermal stability, etc.) of polybenzoxazolimide, which is the final thermoset, may be adversely affected, and the film may be greatly reduced during the heat curing process. Therefore, the content of the DNQ photosensitizer is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass in the positive photosensitive resin composition.

  The film forming step of the positive photosensitive resin composition is preferably performed at 120 ° C. or lower. If this temperature is exceeded, the DNQ photosensitizer may start to thermally decompose. For example, when a film is formed at 60 ° C., a large amount of solvent remains in the coating film. In that case, pre-baking at 80 to 120 ° C. for 1 to 30 minutes prior to the exposure step to remove excess solvent is effective in preventing the swelling of the film and the collapse of the fine pattern during development. The solvent can also be extracted and removed by immersing the coating film in water for 1 to 5 minutes.

  Pattern exposure is performed by irradiating the positive photosensitive resin composition film with g-line, h-line, i-line or mixed line of a high-pressure mercury lamp at room temperature for 5 seconds to 1 hour through a photomask to form an alkaline aqueous solution. Develop with alkali. In the development, usable alkaline aqueous solutions include, for example, organic alkalis such as tetramethylammonium hydroxide (TMAH), triethylamine, ethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. An inorganic alkali is mentioned. In many electronic devices, residual metals may adversely affect electrical characteristics, so organic alkalis are preferably used, and TMAH aqueous solutions usually used in semiconductor processes are preferably used.

  At this time, the concentration of the TMAH aqueous solution is 0.05 to 10% by mass, preferably 0.1 to 5% by mass, and more preferably, the normally used 2.38% by mass aqueous solution is used for 10 seconds to 10 minutes at room temperature. A clear positive pattern can be obtained by developing and rinsing with pure water.

  A water-soluble solvent such as alcohols or glycols can be added to the developer and the rinsing liquid as necessary.

<Method for producing fine pattern of polybenzoxazole imide film>
The fine pattern of the positive photosensitive resin composition film containing the hydroxyamide group-containing alicyclic polyimide formed on the substrate as described above or a precursor thereof in an inert gas atmosphere such as air or nitrogen Or the clear relief pattern of a polybenzoxazole imide film | membrane is obtained by heating at 250-400 degreeC in a vacuum, Preferably it is 270-350 degreeC. In this case, if the temperature is lower than 250 ° C., the ring closure reaction may be incomplete, which is not preferable. If the temperature is higher than 400 ° C., the polybenzoxazole imide may partially be thermally decomposed or melted and the pattern shape may be lost. Absent. The heat curing step is desirably performed in a vacuum or in an inert gas, but may be performed in air if the treatment temperature is not too high.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to these Examples. The physical property values in the following examples were measured by the following methods.

<Infrared absorption spectrum>
Using a Fourier transform infrared spectrophotometer (FT-IR5300 or FT-IR350 manufactured by JASCO Corporation), the infrared absorption spectrum of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride was measured by the KBr method. Moreover, the infrared absorption (FT-IR) spectrum of the hydroxyamide group containing alicyclic polyimide and the polybenzoxazole imide thin film (film thickness of about 5 micrometers) was measured with the transmission method.

^<1 H-NMR spectrum>
A proton nuclear magnetic resonance ( ¹ H-NMR) spectrum of a hydroxyamide group-containing alicyclic tetracarboxylic dianhydride was measured in deuterated dimethyl sulfoxide using a JEOL NMR spectrophotometer (ECP400).

<Differential scanning calorimetry (melting point and melting curve)>
The melting point and melting curve of the monomer synthesized in the present invention were measured using a differential scanning calorimetry (DSC) apparatus (DSC3100) manufactured by Bruker Ax in a nitrogen atmosphere at a heating rate of 5 ° C./min. The higher the melting point and the sharper the melting peak, the higher the purity.

<Intrinsic viscosity: η _inh (dL / g)>
A solution of 0.5% by mass of a hydroxyamide group-containing alicyclic polyimide or polybenzoxazole imide in NMP was measured at 30 ° C. using an Ostwald viscometer.

<Glass transition temperature: Tg (° C.)>
Using a thermomechanical analyzer (TMA4000) manufactured by Bruker Ax, the polybenzoxazole imide film (film thickness: about 20 μm) was measured from a loss peak at a frequency of 0.1 Hz and a heating rate of 5 ° C./min by dynamic viscoelasticity measurement. The glass transition temperature was determined.

<Linear thermal expansion coefficient: CTE (ppm / K)>
The range of 100 to 200 ° C. from 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 by thermomechanical analysis using a Bruker Ax thermomechanical analyzer (TMA4000). The linear thermal expansion coefficient in the film surface direction of a polybenzoxazole imide film (film thickness of about 20 μm) was determined as an average value at.

<5% weight loss temperature: T _d ⁵ (° C.)>
Using a Bruker Ax thermogravimetric analyzer (TG-DTA2000), the initial weight of the polybenzoxazole imide film is reduced by 5% in the temperature rising process at 10 ° C./min in nitrogen or air. The temperature was measured. Higher values indicate higher thermal stability.

<Dielectric constant: ε _cal >
Using an Abbe refractometer (Abbe refractometer 4T, using a sodium lamp, wavelength 589 nm) manufactured by Atago Co., Ltd., a direction perpendicular to the direction (n _in ) parallel to the film surface of the polybenzoxazole imide film (20 μm thickness), that is, a film the refractive index in the thickness direction (n _out) is measured, the following equation based on the average refractive index _{[n av = (2n in + n} out) / 3 ]: polybenzo in 1MHz by ε _cal = 1.1 × n _av ² The dielectric constant (ε _cal ) of the oxazole imide film was calculated.

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

<Water absorption: W _A (%)>
A polybenzoxazole imide film (film thickness: 20 to 30 μm) that has been vacuum-dried at 50 ° C. for 24 hours is immersed in water at 24 ° C. for 24 hours, and then excess water is wiped off with tissue paper. Asked.

<Elastic modulus, breaking strength and 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 test piece (3 mm × 30 mm) of a polybenzoxazole imide film (film thickness: about 20 μm). Then, the elastic modulus was obtained from the initial gradient of the stress-strain curve, and the elongation at break E _b (%) and the breaking strength were obtained from the elongation rate and stress when the film was broken.

<Light transmittance: T% (%)>
Using a UV-visible spectrophotometer (V-530) manufactured by JASCO Corporation, the visible / ultraviolet transmittance of a hydroxyamide group-containing alicyclic polyimide film (film thickness: about 10 μm) is measured in the range of 200 nm to 800 nm, and h-ray The light transmittance at (405 nm) and g-line (435 nm) was determined.

<Synthesis of hydroxyamide group-containing alicyclic tetracarboxylic dianhydride>
Example 1
Nuclear hydrogenated trimellitic anhydride chloride (44 mmol) was dissolved in dehydrated acetone, and the flask was sealed with a septum cap. Next, 20 mmol of 3,3′-diamino-4,4′-dihydroxybiphenylsulfone (hereinafter referred to as ABPS) is taken in another flask, dissolved in dehydrated acetone, and 4.2 mL of propylene oxide as a deoxidizer ( 60 mmol) was added. During this reaction, the total solute concentration was 15% by weight. While cooling in an ice bath in which sodium chloride was dissolved, the nuclear hydrogenated trimellitic anhydride chloride solution was slowly added dropwise to the ABPS solution with a syringe. After completion of dropping, the reaction mixture was stirred for 3 hours. Acetone was distilled off with an evaporator and concentrated. The deposited precipitate was filtered off, and an excessive amount of nuclear hydrogenated trimellitic anhydride chloride was dissolved and removed with toluene and hexane. This was vacuum-dried at 80 ° C. for 12 hours to obtain a white product with a yield of 52%. From the FT-IR spectrum (FIG. 1) and the ¹ H-NMR spectrum (FIG. 2), it was confirmed that the product was a target hydroxyamide group-containing tetracarboxylic dianhydride represented by the following formula (10). It was.

<Synthesis of Imido Group-Containing Alicyclic Dicarboxylic Acid>
(Example 2)
To a solution obtained by dissolving 20 mmol of trans-1,4-cyclohexanediamine in 43 mL of DMAc, 40 mmol of H-TMA powder was added and stirred at room temperature for 12 hours to obtain a uniform solution. To this reaction solution, a mixed solution of 15.1 mL (160 mmol) of acetic anhydride and 6.5 mL (80 mmol) of pyridine was gradually added dropwise with a syringe and stirred at room temperature for 12 hours. The solvent was removed by evaporation and the mixture was concentrated. The precipitated white solid was separated by filtration and vacuum dried at 100 ° C. for 12 hours to obtain a crude product with a yield of 78%. This was recrystallized with a mixed solvent of methanol / water (volume ratio: 1/1), filtered, and dried under vacuum at 100 ° C. for 12 hours to obtain a white product (total yield 67%). From the FT-IR spectrum (FIG. 3) and the ¹ H-NMR spectrum (FIG. 4), it was confirmed that the product was the target imide group-containing alicyclic dicarboxylic acid represented by the following formula (11). In addition, a sharp endothermic peak (melting point) was observed at 273.5 ° C. in the differential scanning calorimetry curve (FIG. 5), indicating extremely high purity.

(Example 3)
In accordance with the method described in Example 2, using 2,2-bis (trifluoromethyl) benzidine (TFMB) instead of trans-1,4-cyclohexanediamine, containing an imide group represented by the following formula (12) An alicyclic dicarboxylic acid was synthesized. The FT-IR spectrum and ¹ H-NMR spectrum are shown in FIGS. 6 and 7, respectively.

<Polymerization of hydroxyamide group-containing alicyclic polyimide precursor, thermal imidization, thermal cyclization, and film property evaluation of polybenzoxazole imide>
Example 4
5 mmol of 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (hereinafter referred to as HFBAPP) is placed in a well-closed sealed reaction vessel equipped with a stirrer and dissolved in NMP sufficiently dehydrated with Molecular Sieves 4A. Then, 5 mmol of hydroxyamide group-containing alicyclic tetracarboxylic dianhydride powder described in Example 1 represented by the above formula (10) was added to this solution. The polymerization reaction was started at a total monomer concentration of 30% by mass. The mixture was stirred at room temperature for 19 hours to obtain a transparent, uniform, and viscous hydroxyamide group-containing alicyclic polyimide precursor (inherent viscosity 0.30 dL / g) varnish. This varnish was refluxed at 160 ° C. for 3 hours in a nitrogen atmosphere to obtain a hydroxyamide group-containing alicyclic polyimide varnish. From the FT-IR spectrum and ¹ H-NMR spectrum of the product isolated as a powder by dripping it into a large amount of methanol, the product was completed only by imidation without the hydroxyamide group being closed. This was confirmed to be a hydroxyamide group-containing alicyclic polyimide. The intrinsic viscosity of the obtained hydroxyamide group-containing alicyclic polyimide was 0.23 dL / g. The hydroxyamide group-containing alicyclic polyimide varnish (solvent: NMP, 20% by weight) did not precipitate or gel when stored at room temperature for 20 days, and showed high solution storage stability. A hydroxyamide group-containing alicyclic polyimide film (film thickness: about 10 μm) obtained by applying this varnish to a glass substrate and drying at 80 ° C. for 2 hours has a cutoff wavelength of 311 nm, i-line (365 nm), h-line ( 405 nm) and g-line (435 nm) showed very high transparency of 73.9%, 80.3%, and 82.1%, respectively. Similarly, after a hydroxyamide group-containing alicyclic polyimide film was formed on a substrate, a hydroxyamide group ring-closing dehydration reaction was performed under reduced pressure at 280 ° C. for 1 hour to obtain a polybenzoxazole imide film having a thickness of about 20 μm. . This film did not break even in the 180 ° bending test and showed flexibility. As a result of dynamic viscoelasticity measurement of this film, a glass transition point was observed at 234 ° C. The linear thermal expansion coefficient was 64.7 ppm / K. The dielectric constant estimated from the average refractive index was 2.82, the birefringence Δn was 0.0002, and the 5% weight loss temperature was 463 ° C. in nitrogen and 405 ° C. in air. Table 1 summarizes these physical property values. FIGS. 8 to 10 show FT-IR spectra of the hydroxyamide group-containing alicyclic polyimide precursor, the hydroxyamide group-containing alicyclic polyimide, and the polybenzoxazole imide thin film, respectively.

(Example 5)
According to the method described in Example 4 except that 4,4′-oxydianiline (hereinafter referred to as 4,4′-ODA) was used instead of HFBAPP as the diamine component, a hydroxyamide group-containing alicyclic polyimide precursor was used. Was subjected to polymerization, imidization, film formation, and thermal cyclization to produce a polybenzoxazole imide film. The intrinsic viscosities of the hydroxyamide group-containing alicyclic polyimide precursor and the hydroxyamide group-containing alicyclic polyimide were 0.30 dL / g and 0.24 dL / g, respectively. The obtained polybenzoxazole imide film was not broken even by a 180 ° bending test and showed flexibility. Similar to the one described in Example 4, the hydroxyamide group-containing alicyclic polyimide film exhibited high transparency. Table 1 shows physical property values.

(Example 6)
Instead of using the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride represented by the formula (10) of the present invention alone as the tetracarboxylic dianhydride component, this and 3,3 ′, 4,4 '-Biphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was used as a copolymerization component (diamine component: 4,4'-ODA), and a hydroxyamide group-containing alicyclic ring according to the method described in Example 4 A polyimide precursor was polymerized, imidized, formed into a film, and thermally cyclized to produce a polybenzoxazole imide film. In this case, the copolymer composition, that is, the molar ratio of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride and ODPA is 50:50. The obtained polybenzoxazole imide film was not broken even by a 180 ° bending test and showed flexibility. Similar to the one described in Example 4, the hydroxyamide group-containing alicyclic polyimide film exhibited high transparency. Table 1 shows physical property values.

(Example 7)
Example 6 (diamine component: 4) except that 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride (hereinafter referred to as 6FDA) was used as a copolymerization component instead of ODPA. , 4′-ODA), a polybenzoxazole imide film was prepared by polymerizing, imidizing, forming a film, and thermally cyclizing a hydroxyamide group-containing alicyclic polyimide precursor. In this case, the copolymer composition, that is, the molar ratio of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride to 6FDA is 50:50. The obtained polybenzoxazole imide film was not broken even by a 180 ° bending test and showed flexibility. Similar to the one described in Example 4, the hydroxyamide group-containing alicyclic polyimide film exhibited high transparency. Table 1 shows physical property values.

(Comparative Example 1)
As described in Example 3, instead of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride described in Example 1, a tetracarboxylic dianhydride represented by the above formula (7), which is a similar compound, was used. According to the method, a hydroxyamide group-containing polyimide outside the scope of the present invention was polymerized. Intrinsic viscosity was 0.27 dL / g. Using this, a film (film thickness of about 10 μm) was produced according to the method described in Example 3, but it was extremely fragile. Further, the light transmittances of the i-line, h-line and g-line of this film were insufficient, 0%, 1.6% and 37.0%, respectively. This is because the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride of the present invention was not used during the polymerization.

<Polybenzoxazoleimide polymerization by polyphosphoric acid method, film formation, and evaluation of film properties>
(Example 8)
In a sealed reaction vessel equipped with a stirrer, 10 mmol of imide group-containing alicyclic dicarboxylic acid described in Example 2 represented by formula (11) and 10 mmol of ABPS are added, and polyphosphoric acid is added so that the monomer concentration becomes 10% by mass. It was. While stirring with a stirrer, the temperature was raised stepwise from 100 ° C. to 10 ° C. in an oil bath (held at each temperature for 10 minutes), and finally held at 200 ° C. for 10 minutes. After completion of the reaction, the reaction mixture was cooled to room temperature, precipitated in water, and washed with a large amount of water until the washing water became neutral. Furthermore, it wash | cleaned with methanol and finally it vacuum-dried at 100 degreeC, and obtained the white precipitation of the polybenzoxazole imide. The intrinsic viscosity of polybenzoxazole imide measured at 30 ° C. in N-methyl-2-pyrrolidone (NMP) was 1.25 dL / g, which was a high polymer. As a result of the solubility test, it showed high solubility in various solvents such as DMAc, DMF, DMSO, GBL, HMPA, and m-cresol in addition to NMP. Next, this polybenzoxazole imide was dissolved in DMAc so that it might become 15 mass%, and the uniform and transparent solution was obtained. This solution was cast on a glass substrate, dried at 80 ° C. for 1 hour, immersed in methanol, and further heat-treated at 280 ° C. for 1 hour in a vacuum to obtain a transparent and flexible polybenzoxazole imide film. Table 2 shows the physical property values. High glass transition temperature, high transparency, and high film toughness were achieved simultaneously. The FT-IR spectrum of this polybenzoxazole imide thin film is shown in FIG.

Example 9
According to the method described in Example 7, except that 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was used instead of ABPS as the bis (o-aminophenol) component, Oxazole imide was polymerized, a film was prepared, and physical properties were evaluated. As a result of the solubility test, it showed high solubility in various solvents such as DMAc, DMF, DMSO, GBL, HMPA, m-cresol, chloroform, tetrahydrofuran, 1,4-dioxane and cyclohexanone in addition to NMP. Table 2 shows the intrinsic viscosity and physical property values. Similar to the polybenzoxazole imide described in Example 8, excellent physical properties were exhibited. The FT-IR spectrum of this polybenzoxazole imide thin film is shown in FIG.

<Positive pattern formation>
(Example 10)
As a diazonaphthoquinone photosensitizer, 2,3,4-tris (1-oxo-2-diazonaphthoquinone-5-sulfoxy) benzophenone (manufactured by Toyo Gosei Co., Ltd.) was used as the diazonaphthoquinone photosensitive varnish of the hydroxyamide group-containing alicyclic polyimide described in Example 4. NT-200) was added and dissolved so as to be 30% by mass based on the actual amount of the hydroxyamide group-containing alicyclic polyimide. This was apply | coated on the glass substrate surface-treated with the silane coupling agent, and it was made to dry in a hot air dryer at 60 degreeC for 2 hours, and the film of the positive photosensitive resin composition with a film thickness of 5 micrometers was obtained. This was pre-baked at 100 ° C. for 10 minutes, and then a 20-line mixed line (irradiation light intensity at 365 nm = about 150 mW / cm ² ) of an epi-illumination type high-pressure mercury lamp (Toscure 251 manufactured by Harrison Toshiba Lighting Co.) was passed through a photomask. Irradiated for 2 seconds. This was developed with a 2.38 wt% TMAH aqueous solution containing 10% by mass of 2-propanol at 23 ° C. for 25 seconds, rinsed with water, dried at 60 ° C. for several minutes, and a clear relief pattern with a line width of 20 μm was obtained. Obtained. Also, no pattern collapse was observed after the thermal cyclization reaction.

2 is an FT-IR spectrum (KBr method) of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride described in Example 1. FIG. 1 is a ¹ H-NMR spectrum of a hydroxyamide group-containing alicyclic tetracarboxylic dianhydride described in Example 1. 2 is an FT-IR spectrum (KBr method) of an imide group-containing alicyclic dicarboxylic acid described in Example 2. 2 is a ¹ H-NMR spectrum of an imide group-containing alicyclic dicarboxylic acid described in Example 2. 2 is a DSC calorimetric curve of an imide group-containing alicyclic dicarboxylic acid described in Example 2. 3 is an FT-IR spectrum of an imide group-containing alicyclic dicarboxylic acid described in Example 3. 2 is a ¹ H-NMR spectrum of an imide group-containing alicyclic dicarboxylic acid described in Example 3. 4 is an FT-IR spectrum of a hydroxyamide group-containing alicyclic polyimide precursor described in Example 4. 4 is an FT-IR spectrum of a hydroxyamide group-containing alicyclic polyimide described in Example 4. 4 is an FT-IR spectrum of the polybenzoxazole imide thin film described in Example 4. 4 is an FT-IR spectrum of the polybenzoxazole imide thin film described in Example 8. 4 is an FT-IR spectrum of the polybenzoxazole imide thin film described in Example 9.

Claims (13)

The following general formula (1):

(In formula (1), A represents a tetravalent aromatic group.) A hydroxyamide group-containing alicyclic tetracarboxylic dianhydride represented by: The following general formula (2):

(In formula (2), B represents a divalent aromatic group or an aliphatic group.) An imide group-containing alicyclic dicarboxylic acid represented by: The following general formula (3) obtained by equimolar polyaddition reaction of the hydroxyamide group-containing alicyclic tetracarboxylic dianhydride according to claim 1 and diamine:

(In formula (3), A represents a tetravalent aromatic group, and B represents a divalent aromatic group or an aliphatic group.) A hydroxyamide group-containing alicyclic group containing a repeating unit represented by Polyimide precursor. The following general formula (4):

(In formula (4), A represents a tetravalent aromatic group and B represents a divalent aromatic group or an aliphatic group.) A hydroxyamide group-containing alicyclic group containing a repeating unit represented by Polyimide. The following general formula (5):

(In Formula (5), A represents a tetravalent aromatic group and B represents a divalent aromatic group or an aliphatic group.) The polybenzoxazole imide containing the repeating unit represented by this.   The hydroxyamide group-containing alicycle according to claim 4, wherein the hydroxyamide group-containing alicyclic polyimide precursor according to claim 3 is subjected to an imidization reaction by heating or using a chemical imidization reagent. A method for producing a polyimide.   5. The hydroxyamide according to claim 4, wherein the imide group-containing alicyclic dicarboxylic acid or derivative thereof according to claim 2 is subjected to equimolar polycondensation reaction with bis (o-aminophenol) or derivative thereof. A method for producing a group-containing alicyclic polyimide.   The hydroxyamide group-containing alicyclic polyimide precursor according to claim 3 or the hydroxyamide group-containing alicyclic polyimide according to claim 4 is subjected to a dehydration ring-closing reaction by heating or using a chemical imidization reagent. The method for producing a polybenzoxazole imide according to claim 5, wherein   The equimolar polycondensation cyclization of the imide group-containing alicyclic dicarboxylic acid or derivative thereof according to claim 2 and bis (o-aminophenol) or derivative thereof in one step at high temperature in the presence of a condensing agent. The method for producing a polybenzoxazole imide according to claim 5, which is reacted.   A positive-type photosensitive resin composition comprising a hydroxyamide group-containing alicyclic polyimide precursor according to claim 3 or a hydroxyamide group-containing alicyclic polyimide according to claim 4 containing a diazonaphthoquinone photosensitizer. object.   The film of the positive photosensitive resin composition according to claim 10 is subjected to pattern exposure and alkali development, and then subjected to a dehydration ring-closing reaction by heating or using a chemical imidization reagent. A method for producing a fine pattern of a polybenzoxazole imide film.   The protective film of the semiconductor element formed by containing the polybenzoxazole imide of Claim 5.   A plastic substrate for display comprising the polybenzoxazole imide according to claim 5.