JP2011118198A - Photosensitive resin composition, article using the same, and method for forming negative pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition giving high solubility contrast regardless to the kind of a polyimide precursor by addition of a smaller amount of a photo-base generator, and thereby, giving a pattern having preferable features while maintaining a sufficient process margin. <P>SOLUTION: The photosensitive resin composition contains a photo-base generator expressed by general formula (1) or (2) and a polyimide precursor. In formulae, R1 and R2 each represent a hydrogen atom, 1-18C alkyl group, 2-18C alkenyl group, 2-18C alkynyl group or 6-12C aryl group; n is an integer of 2 or 3; m is an integer of 3 to 5; and A represents a group expressed by general formula (3) (not shown) or general formula (4) (not shown). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition having excellent resolution, low cost, and a wide range of options applicable to the structure of a polyimide precursor, and in particular, a product or member formed through a patterning process using electromagnetic waves. A polyimide precursor resin composition that can be suitably used as a material (for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material, or an adhesive), and the resin composition was used. The present invention relates to an article and a negative pattern forming method using the resin composition.

Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used as a surface protective film for semiconductor elements, an interlayer insulating film, and an insulating material for electronic components (Non-patent Document 1).
Circuit pattern formation on a semiconductor integrated circuit or printed circuit board is a complicated and diverse process such as film formation of a resist agent on the surface of the material, exposure to a predetermined location, removal of unnecessary portions by etching, etc., cleaning operation of the substrate surface, etc. Therefore, in order to simplify the manufacturing process of the circuit pattern, a heat-resistant photosensitive material that can be used by leaving a necessary portion of the resist as an insulating material after pattern formation by exposure and development is desired. ing. As these materials, heat-resistant photosensitive materials using polyimide as a base polymer have been proposed.

  As such photosensitive polyimide, for example, in Patent Document 1, a system composed of a polyimide precursor and dichromate was first proposed. However, this material has practical advantages such as high photosensitivity and high film forming ability, but lacks storage stability and has the disadvantage that chromium ions remain in polyimide. Did not come. Furthermore, in Patent Document 2, a compound in which a photosensitive group is introduced into a polyamic acid which is a polyimide precursor by an ester bond is added, and in Patent Document 3, an amine compound having a methacryloyl group is added to a polyamic acid in a polyimide precursor. A compound in which an amino group and a carboxyl group are ion-bonded has been introduced. However, the covalent bond type photosensitive polyimide represented by the ester bond has a problem in that the synthesis process is complicated and the cost is increased. In addition, the ion-bonded photosensitive polyimide has a problem that the bonding force between the polyimide skeleton and the photosensitive group is small and the exposed part is dissolved, so that the remaining film ratio is lowered and it is difficult to increase the film thickness. (Non-Patent Document 2). Many of these compounds are organic solvent developable, and in view of cost and environmental burden, compounds that can be developed with an alkaline aqueous solution are more desirable.

  Such a polyimide precursor uses an aromatic monomer as a basic skeleton so as to be excellent in heat resistance and mechanical properties. In general, a polyimide precursor having an aromatic ring as a basic skeleton tends to decrease in transmittance in the ultraviolet-visible region, and is particularly strong in a wavelength region of less than i-line (wavelength: 365 nm), particularly of less than 350 nm. Since it has absorption, translucency is low at the time of ultraviolet-visible light irradiation. For this reason, the photosensitive polyimide has a problem that the photochemical reaction does not proceed sufficiently in the exposed portion, and the sensitivity is low or the shape of the pattern is deteriorated. As the application range of heat-resistant photosensitive materials widens, material requirements are becoming increasingly diverse, and a thick film forming ability is required for photosensitive polyimide. When the formation pattern is a thick film, the problem of low light transmission becomes more serious. Therefore, in order to realize a heat-resistant photosensitive resin excellent in both film physical properties and sensitivity, in the g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm) region, Construction of a photosensitive system having photoreactive activity is indispensable, and in particular, construction of a photosensitive system having photoreactive activity in the g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) regions is desirable.

  In recent years, photobase generators have attracted attention as one of new pattern forming materials (for example, Patent Document 4). However, applying an existing photobase generator to a polyimide precursor system has a problem in the absorption wavelength. That is, many existing photobase generators have an absorption wavelength of less than 350 nm, and when added to a polyimide precursor as an imidization accelerator by photoreaction, the absorption wavelength of the polyimide precursor and the photobase generator overlaps. There is a problem with sensitivity. Therefore, in order to realize a heat-resistant photosensitive resin excellent in both heat resistance, mechanical properties and sensitivity, a wavelength region of 350 nm or more, preferably 400 nm or more, for example, at least an i-line (wavelength: 365 nm) region. In addition, a base generator having photoreactive activity is demanded. Moreover, in the conventional photobase generator, what the basicity of the amine to generate | occur | produce was weak and the activity as a catalyst was higher was desired. Accordingly, there is a demand for a photobase generator that can sensitize light having a wavelength of 350 nm or longer to generate amine having high catalytic activity efficiently.

Japanese Patent Publication No.49-17374 Japanese Patent Publication No.55-30207 JP 54-145794 A JP 2006-189591 A

“Latest Polyimide: Fundamentals and Applications”, ENTS, 2002, p. 327-338 “Latest Trends in Polymer Materials for Electronic Components III”, Sumibe Techno Research, 2004, p. 36-39

  The present invention has been accomplished in view of the above circumstances, and its purpose is to obtain a large solubility contrast regardless of the type of polyimide precursor with the addition of a smaller amount of photobase generator, and as a result, sufficient An object of the present invention is to provide a photosensitive resin composition capable of obtaining a pattern having a good shape while maintaining a sufficient process margin.

  The photosensitive resin composition which concerns on this invention contains the photobase generator represented by General formula (1) or General formula (2), and a polyimide precursor.

（Ｒ^１及びＲ^２は水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基又は炭素数６〜１２のアリール基であり、ｎは２〜３の整数、ｍは３〜５の整数、Ａは一般式（３）又は一般式（４）で表される基である。）

(R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is (An integer of 2-3, m is an integer of 3-5, A is group represented by General formula (3) or General formula (4).)

（Ｒ^３は水素原子、フェニル基、又は炭素数１〜８のアルキル基、或いは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１８のアシル基、ニトロ基、シアノ基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルキルチオ基、水酸基、及びハロゲン原子からなる群から選択される少なくとも１種の置換基を有するフェニル基を表し、Ｒ^４は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１８のアシル基、ニトロ基、シアノ基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルキルチオ基、水酸基又はハロゲン原子を表し、ｑは１〜４の整数、ｑが２〜４の場合、Ｒ^４は同じでも異なってもよい。）

(R ³ is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, carbon From the group consisting of an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, and a halogen atom. Represents a phenyl group having at least one selected substituent, and R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 to 6 carbon atoms. 12 represents an aryl group, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, or a halogen atom, and q is 1 to 4 Integer when q is 2 to 4, ^{R 4} may be the same or different.)

The inventors of the present invention function as a photobase generator in which the compound represented by the general formula (1) or the general formula (2) sensitizes light having a wavelength of 350 nm or more to efficiently generate an amine having high catalytic activity. In addition, by combining with a polyimide precursor, it has been found that a photosensitive polyimide that can achieve high sensitivity can be achieved with the addition of a smaller amount of a photobase generator or with the addition of the same amount as in the past. Invented.
The photobase generator represented by the above formula (1) or formula (2) used in the present invention generates primary amines efficiently by exposure to light having a wavelength of 200 to 500 nm, and by heating. Since amidine having high catalytic activity can be generated, it acts as a very effective photosensitive component for the polyimide precursor whose reaction to the final product is promoted by the action of the base.

  Since the photobase generator has photoreactivity in the wavelength region of 350 nm or more by having the above specific structure, even when combined with a polyimide precursor, the photobase generator is sensitive to the imide by the action of the base only in the exposed part. Can be promoted. As a result, a polyimide pattern having a good shape can be obtained while maintaining a sufficient process margin.

  In the photosensitive resin composition of this invention, it is catalytic activity efficiently that the said photobase generator is a photobase generator represented by General formula (2-1) or General formula (2-2). From the viewpoint of generating a high amine.

（Ａは、上記一般式（３）又は一般式（４）で表される基である。）

(A is a group represented by the general formula (3) or the general formula (4).)

  In the photosensitive resin composition of the present invention, the photobase generator is represented by the formula (1), the general formula (2), the general formula (2-1), or A in the general formula (2-2): The catalytic activity is efficiently a group represented by any one of (3-1) to (3-4) or a group represented by any one of formulas (4-1) to (4-3). From the viewpoint of generating a high amine.

The polyimide precursor used in the photosensitive resin composition of the present invention is a compound that itself promotes the reaction to the final product by the action of the basic substance, and in particular, the final precursor by the action of the basic substance. It is preferable to use a polyimide precursor such as polyamic acid as the compound that promotes the reaction to the product and changes its solubility upon heating. When such a polyimide precursor is used, a photosensitive polyimide resin composition excellent in heat resistance and mechanical properties can be obtained.
According to the present invention, it is possible to obtain a good pattern shape without applying a dissolution inhibitor or a dissolution inhibitor, even for a polyimide precursor that has conventionally been difficult to obtain a solubility contrast between an exposed portion and an unexposed portion. it can.

  In one embodiment of the present invention, irradiation sensitivity can be improved by adding a sensitizer to the photosensitive resin composition.

  In the photosensitive resin composition of the present invention, the typical emission wavelength of a high-pressure mercury lamp, which is a general exposure light source, is that the photobase generator has photodegradability with respect to electromagnetic waves having a wavelength of 350 nm or more. It is preferable from the points of 436 nm, 405 nm, and 365 nm.

  In the photosensitive resin composition of this invention, it is preferable from the point which can achieve high sensitivity that the said photobase generator has photodegradability with respect to the electromagnetic waves with a wavelength of 400 nm or more.

  In the photosensitive resin composition of the present invention, the 5% weight reduction temperature of the photobase generator is 170 ° C. or more, so that the imide is formed on the coating film of the photosensitive resin composition after exposure and before development. It is preferable because the photobase generator becomes difficult to decompose at the temperature of the conversion.

Moreover, since the photosensitive resin composition of the said invention can select the polyimide precursor of a wide structure, the hardened | cured material obtained by it has characteristically polyimides, such as heat resistance, dimensional stability, and insulation. Since the function can be imparted, it is suitable as a film, coating film or three-dimensional structure for all known members to which polyimide is applied.
In particular, the photosensitive composition according to the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film, for example, Suitable for forming color filters, flexible display films, semiconductor devices, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, other optical members, or building materials .

  Furthermore, the present invention provides a printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, a wiring coating, which is at least partially formed by the photosensitive resin composition according to the present invention or a cured product thereof. An article of any of a covering film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, or a building material is provided.

Furthermore, this invention also provides the negative pattern formation method using the said photosensitive resin composition. The negative pattern forming method according to the present invention irradiates the surface of the coating film or molded body made of the photosensitive resin composition with electromagnetic waves in a predetermined pattern, and performs post-treatment (usually heat treatment) as necessary. ) To selectively reduce the solubility of the electromagnetic wave irradiation site of the coating film or molded product, and then developing.
In the negative pattern forming method, the polyimide precursor and the photobase generator are used in combination with the photobase generator as represented by the general formula (1) or the general formula (2). It is possible to form a negative pattern in which development is performed without using a resist film for protecting the surface of the coating film or molded body made of the resin composition from the developer.

  According to the present invention, by adding a smaller amount of photobase generator, a large solubility contrast can be obtained regardless of the type of polyimide precursor, and as a result, a pattern having a good shape can be formed while maintaining a sufficient process margin. The photosensitive resin composition which can be obtained, the pattern formation method using the said photosensitive resin composition, and the articles | goods using the said photosensitive resin composition can be provided.

FIG. 1 is a diagram showing transmittance curves of the filter 1 and the filter 2. FIG. 2 is a graph showing the relationship between the amount of each amine added and the imidization rate.

The present invention includes a photosensitive resin composition using a photobase generator, an article using the photosensitive resin composition, and a negative pattern forming method. Hereinafter, it demonstrates in order from the photosensitive resin composition.
In the present invention, the light and electromagnetic waves that cleave the bond of the photobase generator are not limited as long as they can cause a photodegradation reaction, and include not only electromagnetic waves having wavelengths in the visible and invisible regions, but also electrons. It includes particle beams such as rays, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.

  The photosensitive resin composition of this invention contains the photobase generator represented by General formula (1) or General formula (2), and a polyimide precursor.

（Ｒ^１及びＲ^２は水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基又は炭素数６〜１２のアリール基であり、ｎは２〜３の整数、ｍは３〜５の整数、Ａは一般式（３）又は一般式（４）で表される基である。）

(R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is (An integer of 2-3, m is an integer of 3-5, A is group represented by General formula (3) or General formula (4).)

（Ｒ^３は、水素原子、フェニル基、又は炭素数１〜８のアルキル基、或いは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１８のアシル基、ニトロ基、シアノ基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルキルチオ基、水酸基、及びハロゲン原子からなる群から選択される少なくとも１種の置換基を有するフェニル基を表し、Ｒ^４は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１８のアシル基、ニトロ基、シアノ基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルキルチオ基、水酸基又はハロゲン原子を表し、ｑは１〜４の整数、ｑが２〜４の場合、Ｒ^４は同じでも異なってもよい。）

(R ³ is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, A group consisting of an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, and a halogen atom Represents a phenyl group having at least one substituent selected from R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 carbon atoms. Represents an aryl group having 12 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, or a halogen atom; 4 adjustments , When q is 2 to 4, ^{R 4} may be the same or different.)

  The photobase generator represented by the above formula (1) or formula (2) used in the present invention is sensitive to light having a wavelength of 200 to 500 nm, and efficiently generates a carbamoyl group-containing primary amine, By heating, the carbamoyl group-containing primary amine can be intramolecularly cyclized to generate amidine having high catalytic activity. On the other hand, the polyimide precursor can lower the temperature at which the imidization reaction is initiated, for example, by the catalytic action of a basic substance. In other words, by allowing the polyimide precursor to coexist with the photobase generator and generating a base by irradiation with electromagnetic waves, the site irradiated with electromagnetic waves promotes the reaction to the final product of the polyimide precursor, and more Imidization can proceed at a low temperature. In order to obtain a pattern using the photosensitive resin composition of the present invention, for example, after irradiating an electromagnetic wave to a place where the pattern is to be left, imidization proceeds in a place where the basic substance is present, Heating is performed at a temperature where imidization does not proceed in a place where it does not exist. As a result, since the imidization proceeds only in the place where the basic substance exists, that is, the place irradiated with the electromagnetic wave and the solubility is lowered, by developing with a predetermined developer (organic solvent, alkaline aqueous solution, etc.), A pattern can be obtained. Then, according to the objective, it can heat further and can be set as a polyimide pattern.

As described above, according to the present invention, a novel photobase generator having a photoreactive activity in a wavelength region of 350 nm or more and efficiently generating an amine having high catalytic activity can be used to form a polyimide precursor. A photosensitive polyimide resin composition can be prepared and used by a simple method of mixing additives. The photobase generators represented by the above formulas (1) and (2) generate amidine having high catalytic activity by irradiation with electromagnetic waves and subsequent heating, and therefore various structures having reactions in which the base acts as a catalyst. It can be applied to the polyimide precursor. Therefore, the photosensitive resin composition according to the present invention can be selected from a wide range of final polyimide structures without being limited by the pattern formation process, and is excellent in heat resistance and mechanical properties. Available as a thing.
In particular, since the photobase generator represented by the above formulas (1) and (2) according to the present invention can generate amidine having high catalytic activity, the addition of the base generator in the photosensitive resin composition It is possible to reduce the amount, and since the amount of polyimide can be relatively increased, the physical properties such as reduction of outgas generation, heat resistance and mechanical properties of the polyimide film used as a permanent film are excellent. Become. Alternatively, the sensitivity of the photosensitive resin composition can be improved by using the same amount of base generator as in the prior art.

The photobase generator used in the present invention has photoreactivity in the wavelength region of 350 nm or more by having the above-mentioned specific structure. Therefore, even when combined with a polyimide precursor, the photobase generator has a high sensitivity, and only the exposed part is a base. It is possible to promote imidization by the action of. The photobase generator can have photoreactive activity in a wavelength region of 400 nm or more depending on the substituent to be introduced. In this case, a broad absorption band in the i-line (wavelength: 365 nm) region. Since it functions as a highly sensitive photobase generator without overlapping the absorption wavelength with the polyimide precursor having an aromatic ring having a basic skeleton as an electromagnetic wave on the coating film or molded body of the photosensitive resin composition The solubility difference between the irradiated part and the non-irradiated part can be increased, and as a result, a pattern having a good shape can be obtained while maintaining a sufficient process margin.
According to the present invention, a good pattern shape can be obtained without applying a dissolution inhibitor or a dissolution inhibitor for a polyimide precursor that has conventionally had difficulty in obtaining a solubility contrast between an exposed portion and an unexposed portion. .

Moreover, since the photobase generator used in the present invention does not contain a halogen ion or the like as a counter anion, the photosensitive resin composition of the present invention has no fear of metal corrosion.
Further, since the photobase generator used in the present invention is not basic before exposure, even if it is contained in the reaction composition, the storage stability of the reactive composition is not reduced. . In addition, the photobase generator used in the present invention is stable against heat and hardly generates a base even when heated unless irradiated with light. Therefore, the photosensitive resin composition of the present invention also has an advantage of high storage stability.

First, the photobase generator used in the present invention is described. The photobase generator is a compound that decomposes its chemical structure upon irradiation with light and generates a base (amine).
In the photosensitive resin composition of the present invention, a photobase generator represented by general formula (1) and / or a photobase generator represented by general formula (2) is used.

（Ｒ^１及びＲ^２は水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基又は炭素数６〜１２のアリール基であり、ｎは２〜３の整数、ｍは３〜５の整数、Ａは一般式（３）又は一般式（４）で表される基である。）

(R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is (An integer of 2-3, m is an integer of 3-5, A is group represented by General formula (3) or General formula (4).)

（Ｒ^３は、水素原子、フェニル基、又は炭素数１〜８のアルキル基、或いは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１８のアシル基、ニトロ基、シアノ基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルキルチオ基、水酸基、及びハロゲン原子からなる群から選択される少なくとも１種の置換基を有するフェニル基を表し、Ｒ^４は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１８のアシル基、ニトロ基、シアノ基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルキルチオ基、水酸基又はハロゲン原子を表し、ｑは１〜４の整数、ｑが２〜４の場合、Ｒ^４は同じでも異なってもよい。）

(R ³ is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, A group consisting of an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, and a halogen atom Represents a phenyl group having at least one substituent selected from R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 carbon atoms. Represents an aryl group having 12 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, or a halogen atom; 4 adjustments , When q is 2 to 4, ^{R 4} may be the same or different.)

<General formula (1)>
Among R ¹ and R ² , the alkyl group having 1 to 18 carbon atoms (preferably 1 to 12, more preferably 1 to 8) is a linear alkyl group (methyl, ethyl, n-propyl, n -Butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc., branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl) , Neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridged cyclic alkyl groups (norbornyl, Adamantyl and pinanyl, etc.). R ¹ and R ² may be the same or different. As the alkyl group, in addition to the above, a part of hydrogen atoms of the alkyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and / or Or the substituted alkyl group substituted by the C1-C18 alkylthio group etc. is also contained. Substituted alkyl groups include, for example, arylalkyl groups (such as benzyl).

Among R ¹ and R ² , the alkenyl group having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8) is a linear or branched alkenyl group (vinyl, allyl, 1- Propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl And cycloalkenyl groups (such as -cyclohexenyl and 3-cyclohexenyl). As the alkenyl group, in addition to the above, a part of hydrogen atoms of the alkenyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio having 1 to 18 carbon atoms. Also included are substituted alkenyl groups substituted with groups and the like. Substituted alkenyl groups include, for example, arylalkenyl groups (such as styryl and cinnamyl).

Among R ¹ and R ² , the alkynyl group having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8) is a linear or branched alkynyl group (ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl 1-methyl-2-butynyl, 3-methyl-1-butynyl, 1-decynyl, 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl, 10-dodecynyl and the like. As the alkynyl group, in addition to the above, a part of hydrogen atoms of the alkynyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio having 1 to 18 carbon atoms. Also included are substituted alkynyl groups substituted with groups and the like. Substituted alkynyl groups include, for example, arylalkynyl groups (such as phenylethynyl).

Among R ¹ and R ² , the aryl group having 6 to 14 carbon atoms includes a monocyclic aryl group (such as a phenyl group), a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinonyl, fluorenyl, and naphthoquinolyl). Etc.) and aromatic heterocyclic hydrocarbon groups (ethynyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (derived from pyridine) Group), 9-oxoxanthenyl (group derived from xanthone), 9-oxothioxanthenyl (group derived from thioxanthone) and the like. As the aryl group, in addition to the above, a part of the hydrogen atoms of the aryl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio having 1 to 18 carbon atoms. A substituted aryl group substituted with a group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or the like is also included.

Among R ¹ and R ² , from the viewpoint of ease of cyclization reaction from primary amine to amidine (steric hindrance) and basicity of the generated base, a hydrogen atom and an alkyl group having 1 to 18 carbon atoms are More preferably, it is a linear alkyl group having 1 to 8 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-octyl), particularly preferably methyl and ethyl.

  n is an integer of 2 to 3, and 3 is preferable from the viewpoint of ease of cyclization reaction from primary amine to amidine.

  Preferred examples of the photobase generator represented by the general formula (1) include those represented by any one of the formulas (1-1) to (1-4).

（Ａは、上記一般式（３）又は一般式（４）で表される基である。）

(A is a group represented by the general formula (3) or the general formula (4).)

<General formula (2)>
n is an integer of 2 to 3, and 3 is preferable from the viewpoint of easiness of cyclization reaction from primary amine to amidine.

  m is an integer of 3 to 5, and is preferably 3 or 5 from the viewpoint of the basic strength of the bicyclic amidine produced by cyclization.

  Preferred examples of the photobase generator represented by the general formula (2) include those represented by the formula (2-1) or the formula (2-2).

（Ａは、上記一般式（３）又は一般式（４）で表される基である。）

(A is a group represented by the general formula (3) or the general formula (4).)

<A>
In the general formula (1) or the general formula (2), A is a substituent that absorbs light, and by absorbing light, an A—O—CO—NH— (CH ₂ ) n- moiety. Is decomposed into a compound represented by formula (3 ′) or formula (4 ′), carbon dioxide, and formula (5) or formula (6). And the part of Formula (5) or Formula (6) is generated as a primary amine.

（式中、ｎ、ｍ、Ｒ^１及びＲ^２は一般式（１）及び（２）と同様である。）

(In the formula, n, m, R ¹ and R ² are the same as those in the general formulas (1) and (2).)

R ³ is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, carbon From the group consisting of an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, and a halogen atom. It is a phenyl group having at least one selected substituent. In the phenyl group having the above substituent, when there are a plurality of substituents, the substituents may be the same or different.

Among R ³ , the alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) includes an alkyl group having 1 to 8 carbon atoms among the alkyl groups described for R ¹ and R ² above.

Among R ³ , regarding a phenyl group having a substituent, as an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and an aryl group having 6 to 12 carbon atoms, , The same as described above for R ¹ and R ² are included.
An acyl group is a group formed by removing a hydroxyl group from an organic acid, and has a general formula of RCO- (where R is a hydrogen atom, or an aliphatic, alicyclic, and / or aromatic group. Group). Examples of the acyl group having 1 to 18 carbon atoms include an aroyl group having 7 to 18 carbon atoms such as benzoyl and naphthanoyl, in addition to formyl, acetyl, octadecyloyl and the like.
Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, decyloxy, octadecyloxy and isooctadecyloxy, and examples of the alkylthio group having 1 to 18 carbon atoms include methylthio, ethylthio and octylthio.
Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

  Specific examples of the phenyl group having a substituent include nitrophenyl, methoxyphenyl, ethoxyphenyl, octylphenyl, dimethoxyphenyl, diethoxyphenyl, methoxyethoxyphenyl, methylphenyl, ethylphenyl, vinylphenyl, allylphenyl, Examples include ethynylphenyl, biphenyl, methylthiophenyl, acetylphenyl, benzoylphenyl, hydroxyphenyl and chlorophenyl.

R ³ is preferably a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group, a phenyl group, or a phenyl group having a substituent, and more preferably methyl, ethyl, n-propyl, n-butyl, isopropyl. , Isobutyl, sec-butyl, tert-butyl, nitrophenyl and dinitrophenyl groups, particularly preferably methyl, isopropyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl and 2,6-dinitrophenyl It is.

Among R ⁴ , an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, As the alkoxy group having 1 to 18 carbon atoms, the alkylthio group having 1 to 18 carbon atoms, or the halogen atom, the same ones as described above can be used.

When the substituent (R ⁴ ) is bonded to the benzene ring, the absorption wavelength of the benzene ring can be shifted to the long wavelength side. Depending on the wavelength of light to be used, the substituent (R ⁴ ) necessary for photolysis is appropriately selected to have absorption, thereby improving the efficiency of photodegradability.

The degree to which the absorption wavelength shifts (shift value) varies depending on the type of the substituent (R ⁴ ). For the shift value, refer to the table described in “Organic Chemistry Spectral Identification Method 5th Edition (RMSilverstein, 281, published by Tokyo Kagaku Dojin)” (Original “Spectrometric Identification of Organic Compounds 5th ed” (RMSilverstein, published by John Wiley & Sons in 1991) ").

From the viewpoint of the above shift values and the like, the substituent (R ⁴ ) includes a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and an aroyl group having 7 to 13 carbon atoms (particularly a benzoyl group). Nitro group, cyano group, and aryl group having 6 to 12 carbon atoms are preferable.

Of R ⁴ , an alkoxy group and a nitro group are preferable, and methoxy and nitro are more preferable.

q is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
When q is 2 or more, all R ^{4 s} may be the same, all different, or partly different.

  Preferred examples of the group represented by formula (3) include those represented by formula (3-1) to formula (3-4).

  Preferred examples of the group represented by the formula (4) include those represented by the formulas (4-1) to (4-3).

The photobase generator of the present invention can be obtained, for example, by connecting A—OH {A is a group represented by formula (3) or formula (4)} and a primary amine by a carbamate bond.
Carbamate bonds can be formed by reacting with alcohol (A-OH), primary amine, and carbamate bond forming agents (phosgene, diphosgene, triphosgene, N, N′-carbonyldiimidazole, etc.). (Reaction conditions and the like may be known).
Among the carbamate bond forming agents, N, N′-carbonyldiimidazole is preferable from the viewpoint of safety and the like.

Alcohol (A-OH) can be easily obtained by a known method. For example, 2-nitro-α-alkylbenzyl alcohol is obtained by reacting 2-nitrobenzaldehyde and an alkyl Grignard reagent (1); Benzene and alkanoyl halide (or allyloyl halide) are reacted with each other in the presence of aluminum halide, etc. to form a phenyl alkyl ketone, and then a nitro group is introduced into the benzene ring using a nitrating agent (such as nitric acid), Reduction with a reducing agent (such as sodium tetrahydroborate) to obtain 2-nitro-α-alkylbenzyl alcohol (2); 2-nitrobenzaldehyde is reduced with a reducing agent (such as sodium tetrahydroborate) to give 2-nitro Method for obtaining benzyl alcohol (3); 2-nitrobenzaldehyde and pheny Method of obtaining 2-nitro-α-phenylbenzyl alcohol by reacting with alkali metal (phenyllithium etc.) (4); reacting benzene with alkyl halide in the presence of catalyst (eg aluminum halide) to obtain alkylbenzene Then, a nitro group is introduced into the benzene ring using a nitrating agent (such as nitric acid) and reacted with paraformaldehyde in the presence of a base (such as t-butoxypotassium) to give 2- (2-nitrophenyl) -2- Method (5) for obtaining alkyl ethyl alcohol: benzene and benzyl halide are reacted in the presence of a catalyst (such as aluminum halide) to form diphenylmethane (C ₆ H ₅ —CH ₂ —C ₆ H ₅ ), and then nitration Introducing a nitro group into the benzene ring using an agent (such as nitric acid), and in the presence of a base (such as potassium t-butoxy) It is produced by a method (6) for obtaining 2,2-bis (2-nitrophenyl) ethyl alcohol by reacting with laformaldehyde. Among these methods, the method (2) and the method (4) are preferable from the viewpoint of convenience and the like.

In the methods (1) to (6), 2-nitrobenzaldehyde and benzene are substituents corresponding to formula (3) or formula (4) (R ⁴ ; alkyl group, alkenyl group, alkynyl group, aryl group, nitro group , A cyano group, an alkoxy group, an alkylthio group, an acyl group, a hydroxyl group, or a halogen atom). Nitrobenzaldehyde and benzene having such a substituent (R ⁴ ) can be obtained by a known method.

For example, nitrobenzaldehyde having a nitro group as R ⁴ can be obtained by reacting benzaldehyde with fuming nitric acid. Also, benzene having a nitro group as R ⁴ can be obtained by reacting benzene and nitric acid.

Further, nitrobenzene having an alkoxy group as R ⁴ is obtained by converting phenol into a phenolate using a base (such as sodium hydroxide), then reacting with an alkyl halide to form alkoxybenzene, and then reacting with nitric acid.
Nitrobenzaldehyde and benzene having other substituents (R ⁴ ) may be obtained by a known organic chemical reaction (such as Friedel-Craft reaction) or may be obtained from the market (Wako Pure Chemical Industries, Ltd.). .

The primary amine has a primary amino group (NH ₂ —) and a carbamoyl group (R ² NCO—) in one molecule, and is represented by the following formula (5) or (6). included. N, m, R ¹ and R ² are the same as those in the general formulas (1) and (2).

  The primary amine used to synthesize the photobase generator represented by the general formula (1) is, for example, one amino group obtained by reacting 0.5 equivalent of an ester with 1 equivalent of alkylenediamine. A method for obtaining a carbamoyl group-containing primary amine by protecting the amino group of the carbamoyl group-containing primary amine (acetone, etc.) and then reacting with an alkylating agent (dialkyl sulfate, etc.). It can be obtained by, for example, a method in which the amino group is removed and an N-alkylcarbamoyl group-containing primary amine is obtained.

The primary amine used for synthesizing the photobase generator represented by the general formula (2) is obtained by reacting lactam and alkenenitrile, and then hydrogenating.
The above reaction conditions are the same as the known ranges.

Examples of the ester include an ester represented by R ² COOR ⁵ .
R ² is the same as in general formulas (1) and (2). R ⁵ includes an alkyl having 1 to 8 carbon atoms.
Of the esters, methyl acetic acid, methyl propionic acid, ethyl acetic acid and ethyl propionic acid are preferable, and methyl acetic acid and methyl propionic acid are more preferable.

  The lactam includes a lactam represented by the following formula.

  Among the lactams, 4-pentane lactam, 5-hexane lactam and 6-heptane lactam are preferable, and 4-pentane lactam and 6-heptane lactam are more preferable.

Examples of the alkene nitrile include vinyl nitrile and 2-propylene nitrile.
Of the alkenenitriles, 2-propylenenitrile is preferred.

  The primary amine can also be obtained by hydrolyzing amidine. Examples of the amidine include 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, Sun Apro Co., Ltd., “DBU” is a registered trademark of the company), 1,5-diazabicyclo “4. 3.0 "Non-5-ene (DBN, Sun Apro).

  The photobase generator represented by the general formula (2) is preferably obtained by hydrolyzing amidine, from the viewpoint of ease of synthesis and the like.

  When the photobase generator of the present invention is exposed, a primary amine is produced. Furthermore, amidine can be generated by heating the primary amine.

  The photobase generator represented by the formula (1) or (2) of the present invention desirably absorbs electromagnetic waves having a wavelength of 350 nm or more, and more preferably has absorption of electromagnetic waves having a wavelength of 400 nm or more. . Since polyimide precursors having an aromatic ring as a basic skeleton often have a broad absorption band below 365 nm, when the photobase generator has absorption of electromagnetic waves with wavelengths of 350 nm or more or 400 nm or more. This is because the sensitivity can be improved without the absorption wavelengths of the polyimide precursor and the photobase generator overlapping. Since typical emission wavelengths of a high-pressure mercury lamp, which is a general exposure light source, are 365 nm, 405 nm, and 436 nm, among them, the photobase generator is at least one wavelength among electromagnetic waves having wavelengths of 365 nm, 436 nm, and 405 nm. It is more preferable to have absorption.

Moreover, it is preferable that the photobase generator represented by the formulas (1) and (2) of the present invention has photodegradability with respect to electromagnetic waves having a wavelength of 350 nm or more, and 350 nm to 500 nm. More preferably, it has photodegradability with respect to electromagnetic waves having a wavelength of 400 nm or more, and further 400 nm to 500 nm.
Among these, the photobase generator preferably has not only absorption at at least one of electromagnetic waves having wavelengths of 436 nm and 405 nm, but also photolysis with respect to electromagnetic waves having a wavelength of 405 nm. In some cases, even if absorption occurs at at least one of the electromagnetic waves having wavelengths of 436 nm and 405 nm, the light does not have photodegradability with respect to the electromagnetic waves having such a wavelength.
Whether it has photodegradability with respect to electromagnetic waves having a wavelength of 405 nm is determined by irradiating the photobase generator with a high-pressure mercury lamp through a filter that does not pass i-line (wavelength: 365 nm) at all. This can be determined by observing whether the generator decomposes or whether a basic substance is generated.

  Heating for generating amidine may be performed together with exposure, after exposure, or both. The heating temperature is preferably 50 to 250 ° C., more preferably 80 to 150 ° C., particularly preferably 90 to 140 ° C. from the viewpoint of the progress of the cyclization reaction for generating amidine.

  The heating time is preferably from 1 to 300 minutes, more preferably from 3 to 120 minutes, from the viewpoint of the progress of the cyclization reaction and the energy cost.

  The atmosphere for exposure and heating may be any of reduced pressure, increased pressure, and atmospheric pressure, but atmospheric pressure is preferable from the viewpoint of process simplicity. Further, an inert gas atmosphere may be used.

  Further, the basicity generated by the photolysis reaction of the photobase generators represented by the above formulas (1) and (2) and the photobase generators represented by the above formulas (1) and (2) of the present invention. The substance does not decompose at the heating temperature (temperature of partial imidization for pattern formation) performed on the coating film of the photosensitive resin composition containing the photobase generator of the present invention before development after exposure. It is preferable. Specifically, the temperature when the photobase generator represented by the above formulas (1) and (2) or the basic substance generated by the photolysis reaction is heated to reduce the weight by 5% from the initial weight. (5% weight loss temperature) is 170 ° C., more preferably 200 ° C. or more.

  Furthermore, when the photosensitive resin composition containing the photobase generator of the present invention is used as a product, it is preferable that no amine remains in the photosensitive resin composition. A basic substance that decomposes or volatilizes in the imidization process) is preferable. Specifically, it is preferable that the temperature (50% weight reduction temperature) when the basic substance generated by the photolysis reaction is heated to reduce 50% weight from the initial weight is 400 ° C. or less.

Next, the polyimide precursor will be described.
The polyimide precursor used in the present invention is preferably soluble in any solvent (organic solvent or aqueous solution). If it is soluble in a solvent (an organic solvent or an aqueous solution), the solubility of the polyimide precursor in the solvent is changed, and the soluble solvent is used as a developer. It is possible to perform development with a neutral aqueous solution, an acidic aqueous solution, or a neutral aqueous solution.
Here, the term “soluble in a solvent” specifically means that the dissolution rate of the coating film formed on the substrate at 25 ° C. in the solvent is 100 Å / sec or more. The dissolution rate is more preferably 1000 kg / sec or more.
For example, what is soluble in a basic aqueous solution is specifically that the dissolution rate of a coating film formed on a substrate in a 0.1 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. It is more than sec. The dissolution rate is more preferably 1000 kg / sec or more. Furthermore, the dissolution rate with respect to a 2.38 wt% tetramethylammonium hydroxide aqueous solution, which is a more commonly used developer, is preferably 100 kg / sec or more, and more preferably 1000 kg / sec or more. . When the dissolution rate according to the above definition is less than 100 Å / sec, the development time is delayed, workability and productivity are deteriorated, and it is difficult to obtain a solubility contrast between the exposed and unexposed areas.
Accordingly, the dissolution rate of the photosensitive resin composition of the present invention in a solvent is preferably 100 Å / sec or more, more preferably 1000 Å / sec or more, at 25 ° C. preferable.

  As a specific procedure for measuring the dissolution rate, a polyimide precursor coating film formed on a substrate such as an alkali-free glass was adjusted to 25 ° C. and stirred with a developer (0.1 wt% TMAH). Difference between the initial film thickness and the film thickness measured after being immersed in an aqueous solution or a basic aqueous solution such as a 2.38 wt% TMAH aqueous solution, an organic solvent, etc., rinsed with distilled water and dried. Is the amount of film reduction, and the amount of film reduction divided by the time immersed in the developer is the dissolution rate per unit time at 25 ° C.

In addition, when a photosensitive resin composition is actually used in a predetermined photosensitive pattern forming process in order to obtain sufficient solubility contrast between the exposed part and the unexposed part, pattern exposure, and if necessary The ratio of the solubility of the unexposed part and the exposed part in the developer before the development process obtained by the post-process (usually the heating process) (dissolution rate per unit time in the developer of the unexposed part / exposure part The dissolution rate per unit time in the developer is preferably 10 or more.
The dissolution rate per unit time is determined in the same manner as in the above method. After the pattern exposure is performed on the coating film of the photosensitive resin composition and the heating after the exposure is performed, the dissolution rate of the exposed area and the unexposed area is determined. For each.

In the present invention, a polyimide precursor whose reaction to the final product is promoted by the action of a basic substance is used. Here, the mode in which the reaction to the final product is promoted by the action of the basic substance is not only the mode in which the polyimide precursor is changed to the final product only by the action of the basic substance, An embodiment is included in which the reaction temperature of the polyimide precursor to the final product is lowered by the action of the basic substance as compared to the case where the action of the basic substance is not caused.
If there is a reaction temperature difference due to the presence or absence of such a basic substance, the reaction temperature difference can be used to obtain an appropriate temperature at which only the polyimide precursor coexisting with the basic substance reacts with the final product. By heating, only the polyimide precursor coexisting with the basic substance reacts with the final product, and the solubility in a solvent changes. Therefore, the solubility of the polyimide precursor in a certain solvent can be changed depending on the presence or absence of the basic substance, and consequently, patterning by development using the solvent as a developer becomes possible. Therefore, as the polyimide precursor used in the present invention, a polyimide precursor whose reaction to the final product is promoted by the action of a basic substance and whose solubility is lowered by heating compared to before heating is suitable. Used for.

  Here, as a polyimide precursor, the polyimide precursor represented by following formula (I) is mentioned.

（式（Ｉ）中、Ｒ^１１は４価の有機基である。Ｒ^１２は２価の有機基である。Ｒ^１３及びＲ^１４は、水素原子、又は１価の有機基である。ｎは１以上の自然数である。）

(In formula (I), R ¹¹ is a tetravalent organic group. R ¹² is a divalent organic group. R ¹³ and R ¹⁴ are a hydrogen atom or a monovalent organic group. N is (It is a natural number of 1 or more.)

Examples of the case where R ¹³ and R ¹⁴ are monovalent organic groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and C _n H _2n OC _m H _{2m + 1} containing an ether bond therein. The structure represented can be mentioned.

  As the polyimide precursor, a polyamic acid represented by the following formula (II) is preferably used from the viewpoint of alkali developability.

（式（ＩＩ）中、Ｒ^１１は４価の有機基である。Ｒ^１２は２価の有機基である。ｎは１以上の自然数である。）

(In Formula (II), R ¹¹ is a tetravalent organic group. R ¹² is a divalent organic group. N is a natural number of 1 or more.)

In formulas (I) and (II), tetravalent R ¹¹ represents a tetracarboxylic acid residue derived from an acid dianhydride or the like, and divalent R ¹² represents a diamine residue. Incidentally, tetravalent R ¹¹ represents only valence for bonding with the acid, but may have further substituents other. Similarly, the divalent value of R ¹² indicates only the valence for bonding with the amine, but may have other substituents.
Polyamic acid is preferable because it can be obtained by simply mixing acid dianhydride and diamine in a solution, so that it can be synthesized by a one-step reaction, and can be synthesized easily and at low cost.

  When using a polyimide precursor whose thermosetting temperature is lowered by the catalytic action of a base, such as a polyamic acid, first, a photosensitive resin composition in which such a polyamic acid is combined with the photobase generator is applied. Irradiate an electromagnetic wave to the portion of the film or molded body where the pattern is to be left. Then, a basic substance is generated in the irradiated portion, and the imidization temperature of that portion is selectively lowered. Next, the irradiated part undergoes an imidization reaction, while the non-irradiated part is heated at a processing temperature at which the imidization reaction does not occur, and only the irradiated part is partially imidized to the extent that it does not dissolve in the developer. Next, a non-irradiated portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete imidization. Through the above steps, a desired two-dimensional resin pattern (general plane pattern) or three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

In the present invention, the base generator represented by the above formulas (1) and (2) has a high catalytic activity or functions as a highly sensitive photobase generator, and the coating film of the photosensitive resin composition or Since the difference in solubility between the electromagnetic wave irradiation site and the non-irradiation site on the molded body can be increased, excellent developability can be obtained even when a basic aqueous solution is used instead of an organic solvent.
As a secondary effect, when the polyimide precursor to be used is a polyamic acid, it is sufficient that the temperature required for imidization is low due to the catalytic effect of the basic substance. It can be lowered to below ℃. In order to imidize the conventional polyamic acid, the final cure temperature was required to be 300 ° C. or higher, so the use was limited. Applicable to usage.

In addition, regarding the polyimide precursor, for applications where the heat resistance and dimensional stability of the finally obtained polyimide are severe, the part derived from acid dianhydride has an aromatic structure, and the part derived from diamine Is preferably a wholly aromatic polyimide precursor containing an aromatic structure. Therefore, the structure derived from the diamine component is also preferably a structure derived from an aromatic diamine.
Here, the wholly aromatic polyimide precursor is a polyimide precursor obtained by copolymerization of an aromatic acid component and an aromatic amine component, or polymerization of an aromatic acid / amino component, and a derivative thereof. The aromatic acid component is a compound in which all four acid groups forming the polyimide skeleton are substituted on the aromatic ring, and the aromatic amine component is the two amino groups forming the polyimide skeleton. Both are compounds substituted on the aromatic ring, and the aromatic acid / amino component is a compound in which both the acid group and amino group forming the polyimide skeleton are substituted on the aromatic ring. However, as is clear from the specific examples of raw materials described later, it is not necessary that all acid groups or amino groups exist on the same aromatic ring.

  As a method for producing the polyimide precursor of the present invention, a conventionally known method can be applied. For example, (1) A technique of synthesizing a polyamic acid as a precursor from an acid dianhydride and a diamine. (2) A polyimide precursor is synthesized by reacting a carboxylic acid such as an ester acid or an amic acid monomer with a monohydric alcohol, an amino compound, or an epoxy compound synthesized with an acid dianhydride. However, the method is not limited to this.

  Examples of the acid dianhydride applicable to the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane tetracarboxylic dianhydride. , Aliphatic tetracarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′ , 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 , 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride , Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1, 1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, , 3-bis [( , 4-Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2- Dicarboxy) phenoxy] phenyl} propane dianhydride,

2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarbo Cis) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) Phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetraca Boronic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic Acid dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride , Aromatic tetra such as m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride Examples thereof include carboxylic dianhydrides. These may be used alone or in combination of two or more. And as a particularly preferred tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  When acid dianhydride into which fluorine is introduced or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.

  On the other hand, the amine component can also be used alone or in combination of two or more diamines. The diamine component used is not limited, but p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -Diaminodiph Nylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2 -Di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1 -Phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis ( 3-Aminophenoxy) benzene, 1,3 Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis ( 4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dito Trifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2 , 6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-amino) Phenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzen) ) Phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4 , 4′-Dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) -3,3 Like 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane Aromatic amines;

  1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω -Bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [ 2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane Ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12 An aliphatic amine such as diaminododecane;

1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4 -Di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] Alicyclic diamines such as heptane. Examples of guanamines include acetoguanamine, benzoguanamine, and the like, and some or all of the hydrogen atoms on the aromatic ring of the diamine are fluoro group, methyl group, methoxy group, trifluoromethyl group, or trifluoromethoxy group. Diamines substituted with substituents selected from the group can also be used.
Furthermore, depending on the purpose, any one or two or more of ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate group, and isopropenyl group serving as a crosslinking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient. Examples of rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like can be mentioned.
In addition, diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring, for example, Some are represented by the following formula (III). Specific examples include benzidine and the like.

（ａは１以上の自然数、アミノ基はベンゼン環同士の結合に対して、メタ位または、パラ位に結合する。）

(A is a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.)

Furthermore, in the above formula (III), a diamine having a substituent at a position where the amino group on the benzene ring is not substituted and which does not participate in the bond with other benzene rings can also be used. These substituents are monovalent organic groups, but they may be bonded to each other.
Specific examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino. Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl and the like can be mentioned.
When the finally obtained polyimide is used as an optical waveguide or an optical circuit component, the transmittance for electromagnetic waves having a wavelength of 1 μm or less can be improved by introducing fluorine as a substituent of the aromatic ring.

On the other hand, when a diamine having a siloxane skeleton such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane is used as the diamine, the elastic modulus of the finally obtained polyimide is lowered and the glass transition temperature is lowered. be able to.
Here, the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance. However, depending on the desired physical properties, the diamine may be an aliphatic diamine or siloxane within a range not exceeding 60 mol%, preferably not exceeding 40 mol%. Non-aromatic diamines such as diamines may be used.

On the other hand, in order to synthesize a polyimide precursor, for example, while cooling a solution prepared by dissolving 4,4′-diaminodiphenyl ether as an amine component in an organic polar solvent such as N-methylpyrrolidone, an equimolar amount of 3,4 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is gradually added and stirred to obtain a polyimide precursor solution.
The polyimide precursor thus synthesized should have a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide obtained is required to have heat resistance and dimensional stability. Is preferred. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure The proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and particularly preferably wholly aromatic polyimide.

In order to increase the sensitivity when the polyimide precursor is used as a photosensitive resin composition and obtain a pattern shape that accurately reproduces the mask pattern, at least 5% or more of the exposure wavelength when the film thickness is 5 μm. It preferably exhibits a transmittance, and more preferably exhibits a transmittance of 15% or more.
That the transmittance | permeability of a polyimide precursor is high with respect to exposure wavelength means that there is little loss of light, and a highly sensitive photosensitive resin composition can be obtained.

  In addition, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a transmittance with respect to an electromagnetic wave having a wavelength of at least 365 nm, 405 nm, and 436 nm is formed on a film having a thickness of 5 μm. Is preferably 5% or more, more preferably 15%, and still more preferably 50% or more.

The weight average molecular weight of the polyimide precursor is preferably in the range of 3,000 to 1,000,000, more preferably in the range of 5,000 to 500,000, although it depends on the application. More preferably, it is in the range of 1,000,000 to 500,000. When the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when heat treatment or the like is performed to obtain a polymer such as polyimide. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases and the solubility decreases, so that it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.
The molecular weight used here refers to a value in terms of polystyrene by gel permeation chromatography (GPC), may be the molecular weight of the polyimide precursor itself, or after chemical imidization treatment with acetic anhydride or the like. Things can be used.

  The solvent for the synthesis of the polyimide precursor is preferably a polar solvent, and representative examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl. Acetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethylphosphoamide, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, There are cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like, and these solvents are used alone or in combination of two or more. In addition to these, non-polar solvents such as benzene, benzonitrile, 1,4-dioxane, tetrahydrofuran, butyrolactone, xylene, toluene, cyclohexanone, and the like can be used as a solvent. It is used as a reaction regulator, a volatilization regulator of a solvent from the product, a film smoothing agent, and the like.

The photosensitive resin composition according to the present invention may be a simple mixture of only the photobase generator, the polyimide precursor, and a solvent, and further, a sensitizer, a light or thermosetting component, A photosensitive resin composition may be prepared by blending a non-polymerizable binder resin other than the polyimide precursor and other components.
Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition. Moreover, when using polyamic acid as a polyimide precursor, you may use the solution obtained by the synthesis reaction of polyamic acid as it is, and may mix other components there as needed.

When there is a portion where the absorption wavelength of the photobase generator overlaps with the absorption wavelength of the polyimide precursor, and sufficient sensitivity cannot be obtained, addition of a sensitizer may be effective as a means for improving sensitivity. . Even when the photobase generator has an absorption wavelength in the wavelength band of electromagnetic waves that pass through the polyimide precursor, a sensitizer can be added as a means for improving sensitivity. However, it is necessary to take into consideration the film physical properties of the resulting pattern, particularly the decrease in film strength and heat resistance, accompanying the decrease in the content of the polyimide precursor due to the addition of a sensitizer.
Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, cyanine and derivatives thereof, merocyanine and derivatives thereof, coumarins and derivatives thereof, ketocoumarins and derivatives thereof, and ketobiscoumarins. And derivatives thereof, cyclopentanone and derivatives thereof, cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, quinoline derivatives and derivatives thereof, styrylquinoline derivatives and derivatives thereof, thioxanthene derivatives, xanthene derivatives and Derivatives, oxonol-based and derivatives thereof, rhodamine-based and derivatives thereof, pyrylium salts and derivatives thereof.

Specific examples of cyanine, merocyanine and derivatives thereof include 3,3′-dicarboxyethyl-2,2′thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide, 1,3′-diethyl-2,2′-quinothiocyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolidene) ethylidene] -2-thioxo-4- And oxazolidine.
Specific examples of coumarin, ketocoumarin and derivatives thereof include 3- (2′-benzimidazole) -7-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylaminocoumarin), and 3,3′-carbonylbiscoumarin. 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin) and the like.
Specific examples of thioxanthone and derivatives thereof include diethyl thioxanthone and isopropyl thioxanthone.

Other examples include benzophenone, acetophenone, anthrone, p, p'-tetramethyldiaminobenzophenone (Michler ketone), phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-acetyl-p-nitroaniline, p-nitro. Aniline, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, N-acetyl-4-nitro-1-naphthylamine, picramide, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9- Benzanthrone, p, p′-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, 1,2-naphthoquinone, 2,5-bis- (4′-diethylaminobenzal) -cyclopentane, 2,6-bis- (4′-diethyla Minobenzal) -cyclohexanone, 2,6-bis- (4′-dimethylaminobenzal) -4-methyl-cyclohexanone, 2,6-bis- (4′-diethylaminobenzal) -4-methyl-cyclohexanone, 4, 4'-bis- (dimethylamino) -chalcone, 4,4'-bis- (diethylamino) -chalcone, p-dimethylaminobenzylideneindanone, 1,3-bis- (4'-dimethylaminobenzal) -acetone 1,3-bis- (4′-diethylaminobenzal) -acetone, N-phenyl-diethanolamine, Np-tolyl-diethylamine, and the like.
In the present invention, one or more of these sensitizers can be used.

Examples of the solvent used in the composition include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether, ethylene glycol Glycol monoethers such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (so-called cellosolves); methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; ethyl acetate, acetic acid Chill, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, Esters such as dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, Halogenated hydrocarbons such as 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N- Amides such as methylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide; Pyrrolidones such as N-methylpyrrolidone; Lactones such as γ-butyrolactone; Sulfoxides such as dimethylsulfoxide And other organic polar solvents, and aromatic hydrocarbons such as benzene, toluene, and xylene, and other organic nonpolar solvents. These solvents are used alone or in combination.
Among them, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexa Polar solvents such as methylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone It is mentioned as a suitable thing.

  As the photocurable component, a compound having one or more ethylenically unsaturated bonds can be used. For example, an amide monomer, a (meth) acrylate monomer, a urethane (meth) acrylate oligomer, a polyester (meth) Aromatic vinyl compounds such as acrylate oligomers, epoxy (meth) acrylates, hydroxyl group-containing (meth) acrylates, and styrene can be exemplified. In addition, when the polyimide precursor has a carboxylic acid component such as polyamic acid in the structure, the use of an ethylenically unsaturated bond-containing compound having a tertiary amino group causes the carboxylic acid of the polyimide precursor to have an ionic bond. When the photosensitive resin composition is formed, the contrast of the dissolution rate of the exposed area and the unexposed area is increased.

  When using a photocurable compound having such an ethylenically unsaturated bond, a photoradical generator may be further added. Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethyl Thioxanthone such as luthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylpyroxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, etc. Monoacylphosphine oxides or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones.

  In order to impart processing characteristics and various functionalities to the resin composition according to the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

In the photosensitive resin composition according to the present invention, the polyimide precursor (solid content) is obtained with respect to the entire solid content of the photosensitive resin composition from the viewpoint of film physical properties of the pattern obtained, particularly film strength and heat resistance. It is preferable to contain 30% by weight or more and 50% by weight or more. Moreover, the photobase generator represented by the formulas (1) and (2) is usually 0.01 to 50 parts by weight with respect to 100 parts by weight of the solid content of the polyimide precursor contained in the photosensitive resin composition. The content is preferably within the range of 0.1 to 30 parts by weight. If the amount is less than 0.01 part by weight, the effect of promoting the cyclization reaction of the polyimide precursor tends to be insufficient, and if it exceeds 50 parts by weight, it is difficult to satisfy various physical properties required for the finally obtained resin cured product. .
Moreover, it is preferable to set it as less than 50 weight part with respect to 100 weight part of solid content of a polyimide precursor, and, as for the compounding quantity of the said sensitizer, it is more preferable to set it as less than 30 weight part. Further, in order to prevent deterioration of various physical properties required for the finally obtained cured resin, the total of the photobase generator and the sensitizer represented by the formulas (1) and (2) according to the present invention is polyimide. The amount is desirably 50 parts by weight or less with respect to 100 parts by weight of the precursor.
The mixing ratio of other optional components is preferably in the range of 0.1% by weight to 20% by weight with respect to the entire solid content of the photosensitive resin composition. When the content is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when the content exceeds 20% by weight, the properties of the finally obtained resin cured product are hardly reflected in the final product. In addition, solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

  The photosensitive resin composition according to the present invention can be used in various coating processes and molding processes to produce films and molded articles having a three-dimensional shape.

The polyimide obtained from the photosensitive resin composition of the present invention is good because the original properties such as heat resistance, dimensional stability and insulation are not impaired.
For example, the 5% weight loss temperature measured in nitrogen of polyimide obtained from the photosensitive resin composition of the present invention is preferably 250 ° C. or higher, more preferably 300 ° C. or higher. In particular, when used in applications such as electronic parts that pass through the solder reflow process, if the 5% weight loss temperature is 300 ° C. or less, defects such as bubbles occur due to the decomposition gas generated in the solder reflow process. There is a fear.
Here, the 5% weight reduction temperature is the time when the weight of the sample is reduced by 5% from the initial weight when the weight reduction is measured using a thermogravimetric analyzer (in other words, the sample weight becomes 95% of the initial weight). Temperature). Similarly, the 10% weight reduction temperature is a temperature at which the sample weight is reduced by 10% from the initial weight.

  The glass transition temperature of the polyimide obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance. However, in applications where a thermoforming process is considered, such as an optical waveguide, 120 ° C. to 450 ° C. It is preferable to show a glass transition temperature of about ° C, and more preferable to show a glass transition temperature of about 200 ° C to 400 ° C. Here, the glass transition temperature in the present invention is tan δ (tan δ = loss elastic modulus (E ″)) by dynamic viscoelasticity measurement when the polyimide obtained from the photosensitive resin composition can be formed into a film shape. / Storage elastic modulus (E ′)) is determined from the peak temperature. The dynamic viscoelasticity measurement can be performed, for example, with a viscoelasticity measuring apparatus Solid Analyzer RSA II (manufactured by Rheometric Scientific) at a frequency of 3 Hz and a temperature rising rate of 5 ° C./min. When the polyimide obtained from the photosensitive resin composition cannot be formed into a film shape, the determination is made based on the temperature at the inflection point of the baseline of the differential thermal analyzer (DSC).

From the viewpoint of dimensional stability of the polyimide obtained from the photosensitive resin composition of the present invention, the linear thermal expansion coefficient is preferably 60 ppm or less, and more preferably 40 ppm or less. In the case of forming a film on a silicon wafer in a manufacturing process of a semiconductor element or the like, 20 ppm or less is more preferable from the viewpoint of adhesion and warpage of the substrate. Here, the linear thermal expansion coefficient in this invention can be calculated | required with the thermomechanical analyzer (TMA) of the film of the polyimide obtained from the photosensitive resin composition obtained by this invention. Using a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku Corporation)), the heating rate is 10 ° C./min, and the tensile load is 1 g / 25000 μm ² so that the weight per cross-sectional area of the evaluation sample is the same. It is done.

As described above, in the photosensitive polyimide resin composition according to the present invention, the photobase generator represented by the above formulas (1) and (2) has high catalytic activity or high sensitivity photobase generation. By functioning as an agent, a wide variety of polyimide precursors can be applied, and the final polyimide structure can be selected from a wide range.
Moreover, according to this invention, the photosensitive polyimide resin composition is obtained by the simple method of mixing only the photobase generator represented by Formula (1), (2) concerning the said invention to the polyimide precursor. Because it is possible, it is excellent in cost performance.
Furthermore, due to the catalytic effect of amine and amidine generated by irradiation of electromagnetic waves, the processing temperature required for the reaction to the final product such as imidization can be reduced, thereby reducing the inability to process and damage to the product due to heat. It is possible.

  The photosensitive resin composition according to the present invention is a known resin material such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical member. Can be used in all fields and products.

  The photosensitive resin composition according to the present invention is used in a wide range of fields and products in which properties such as heat resistance, dimensional stability, and insulation are effective, such as paints or printing inks, color filters, and films for flexible displays. It is preferably used as a material for forming semiconductor devices, electronic parts, interlayer insulating films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members, or building materials. Specific examples include buffer coating films for semiconductor devices, interlayer insulating films of multilayer wiring boards, and the like.

  In particular, the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film made of polyimide. Suitable for forming color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, other optical members or electronic members, for example ing.

  Further, in the present invention, a printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, which is at least partly formed by the photosensitive resin composition according to the present invention or a thermoset thereof, An article of any one of a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, and a building material is provided.

Next, the negative pattern forming method according to the present invention will be described.
In the negative pattern forming method according to the present invention, the surface of the coating film or molded body made of the photosensitive resin composition according to the present invention is irradiated with electromagnetic waves in a predetermined pattern, and after heat treatment or the like as necessary. It develops, after processing, selectively reducing the solubility of the electromagnetic wave irradiation site | part of the said coating film or a molded object, It is characterized by the above-mentioned.
When the photosensitive resin composition according to the present invention is applied on a support and is irradiated with electromagnetic waves in a predetermined pattern, the photobasic substance is decomposed and a basic substance is generated only in the exposed portion. The basic substance acts as a catalyst that promotes the reaction of the polyimide precursor in the exposed area to the final product.

  When the basic substance reacts directly with the polyimide precursor of the exposed part to the final product and only the polyimide precursor of the exposed part is selectively reduced in solubility in a certain solvent, It is possible to perform development by dissolving only the unexposed part where the solubility is not lowered without using post-processing and using the solvent having the lowered solubility of the exposed part as a developer.

  The photosensitive resin composition of the present invention includes N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N- Dimethyl methoxyacetamide, dimethyl sulfoxide, hexamethylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl- After being dissolved in a polar solvent such as γ-butyrolactone, it is applied to the surface of a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by dipping, spraying, screen printing, spin coating, etc. Removing part More, it is possible to provide a tack-free coating on the substrate surface. Although there is no restriction | limiting in particular in the thickness of a coating film, it is preferable that it is 0.5-50 micrometers, and it is more desirable that it is 1.0-20 micrometers from a sensitivity and a development speed surface. As drying conditions of the apply | coated coating film, 80-100 degreeC and 1 minute-20 minutes are mentioned, for example.

  This coating film is irradiated with electromagnetic waves through a mask having a predetermined pattern, and is exposed to a pattern. After heating, the unexposed portion of the film is developed and removed with an appropriate developer to obtain a desired pattern. A patterned film can be obtained.

  The exposure method and exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure, and may be a g-line stepper, an i-line stepper, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, Alternatively, a projector or a radiation source that can irradiate other ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

In the negative pattern forming method according to the present invention, it is preferable to perform post-treatment such as heat treatment during the exposure step and / or between the exposure step and the development step. The post-treatment here is a treatment for intramolecular cyclization of the carbamoyl group-containing primary amine generated from the photobase generator by exposure to amidine, and the electromagnetic wave irradiation site of the coating film or molded product, This is a process for selectively reducing the solubility in a certain solvent.
The post-treatment such as heat treatment is, for example, a treatment in which only the polyimide precursor in the exposed portion coexisting with the basic substance is reacted with the final product. Accordingly, when heat treatment is performed, for example, it may be performed at a temperature at which the cyclization rate of the polyimide precursor becomes different between the exposed portion where the basic substance is present and the unexposed portion where the basic substance is not present. preferable.

For example, when polyamic acid is imidized, the preferable temperature range of the heat treatment at this stage is usually about 60 ° C to 200 ° C. If the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to create a difference in the imidization ratio between the exposed and unexposed areas under realistic process conditions. On the other hand, if the heat treatment temperature is 200 ° C. or higher, a neutral compound that generates a basic substance is thermally decomposed by an intramolecular cleavage reaction accompanying absorption of electromagnetic waves, or even in an unexposed area where no amine is present. Due to the progress of imidization, a difference in solubility between the exposed portion and the unexposed portion is difficult to occur.
Specifically, for example, heating is performed at 120 to 200 ° C. for 1 minute to 20 minutes.
This heat treatment may be any method as long as it is a known method, and specific examples thereof include, but are not particularly limited to, heating with a circulating oven under a nitrogen atmosphere or a hot plate.

The developer used in the development step is not particularly limited, and can be appropriately selected according to the polyimide precursor to be used, such as a basic aqueous solution or an organic solvent.
The basic aqueous solution is not particularly limited. For example, in addition to an aqueous tetramethylammonium hydroxide (TMAH) solution having a concentration of 0.01% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight, diethanolamine is used. , Diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, Examples include aqueous solutions of cyclohexylamine, ethylenediamine, hexamethylenediamine, tetramethylammonium, and the like.
The solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.
The organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, Add alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of two or more. May be. After development, wash with water. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.

  After development, if necessary, rinse with water or a poor solvent and dry at 80 to 100 ° C. to stabilize the pattern. In order to make this relief pattern heat resistant, the imidization proceeds completely by heating at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several hours to complete patterning. A high heat resistant resin layer is formed.

<Synthesis Example 1>
Synthesis of 4,5-dimethoxy-2-nitrobenzyl alcohol In a 500 ml Meyer flask, 9.0 g of 4,5-dimethoxy-2-nitrobenzaldehyde (Wako Pure Chemical Industries, Ltd.) and sodium tetrahydroborate (Wako Pure Chemical Industries, Ltd.) Company) 1.7 g and 400 ml of methanol were added and stirred at room temperature (about 25 ° C.) for 3 hours. It became liquid. To this yellow suspension, 200 ml of chloroform was added for extraction, the organic layer was separated, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a pale yellow solid. This solid was dissolved in 30 ml of ethyl acetate and recrystallized to obtain 8.0 g of pale yellow crystals.
As a result of analysis by ¹ H-NMR, it was confirmed that the pale yellow crystals were 4,5-dimethoxy-2-nitrobenzyl alcohol.

<Synthesis Example 2>
Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol (1) Synthesis of 4,5-dimethoxy-2-nitroacetophenone (Intermediate 1) 90 ml of concentrated nitric acid was placed in a 200 ml Meyer flask and cooled in a cold water bath. While maintaining the temperature in the system at 18 to 22 ° C., 15.0 g of 4,5-dimethoxyacetophenone (Wako Pure Chemical Industries, Ltd.) was added over 1 hour, followed by stirring at the same temperature for 1 hour, and the reaction solution Was added dropwise to a 3 L beaker containing 1200 ml of water over 30 minutes with stirring to deposit a pale yellow solid. This solid was subjected to suction filtration to obtain a pale yellow solid. This pale yellow solid was dissolved in 250 ml of ethanol and recrystallized to obtain 8.4 g of pale yellow needle crystals (intermediate 1).
As a result of analysis by ¹ H-NMR, it was confirmed that this pale yellow needle-like crystal was 4,5-dimethoxy-2-nitroacetophenone (intermediate 1).

(2) Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol In a 500 ml Meyer flask, 10.0 g of (Intermediate 1), 1.7 g of sodium tetrahydroborate and 400 ml of methanol were placed at room temperature (approximately After stirring at 25 ° C. for 3 hours, the obtained reaction solution was dropped into a 3 L beaker containing 400 ml of water with stirring to obtain a yellow suspension. To this yellow suspension, 200 ml of chloroform was added for extraction, the organic layer was separated, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a pale yellow solid. This pale yellow solid was dissolved in 30 ml of ethyl acetate and recrystallized to obtain 8.6 g of pale yellow crystals.
As a result of analysis by ¹ H-NMR, it was confirmed that the pale yellow crystals were 1- (4,5-dimethoxy-2-nitrophenyl) ethanol.

<Synthesis Example 3>
Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol (1) Synthesis of 1- (3,4-dimethoxyphenyl) -2-methyl-propanone (Intermediate 2) Dropping funnel 4. A 500 ml three-necked glass flask equipped with a thermometer and a magnetic stirrer was purged with nitrogen, and 6.68 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.), 1,2-dimethoxybenzene (Wako Pure Chemical Industries, Ltd.) 5. 52 g and 30 ml of dichloromethane were charged and cooled in an ice bath while stirring with a magnetic stirrer to obtain a mixed solution of 0 to 5 ° C.
On the other hand, 4.50 g of isobutyryl chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 ml of dichloromethane to obtain a dichloromethane solution of isobutyryl chloride.

While maintaining the temperature of the previous mixture at 0 to 5 ° C. in an ice bath, the dichloromethane solution was added dropwise to the mixture over 30 minutes from the dropping funnel, and then the ice bath was removed and room temperature (about 25 ° C. ) For 2 hours. Thereafter, 40 ml of 2N hydrochloric acid, 100 ml of water and 100 g of dichloromethane were added to the reaction solution and stirred for 30 minutes, and the organic layer was separated. The organic layer was washed 3 times with 200 ml of water, the solvent was distilled off under reduced pressure with a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 7.56 g of a yellow oil (intermediate 2). It was.
As a result of analysis by ¹ H-NMR, it was confirmed that this yellow oily substance was 1- (3,4-dimethoxyphenyl) -2-methyl-propanone (intermediate 2).

(2) Synthesis of 1- (3,4-dimethoxy-2-nitrophenyl) -2-methyl-propanone (Intermediate 3) In Synthesis Example 2 (1), “4,5-dimethoxyacetophenone 15.0 g” was changed to “ 16.0 g of pale yellow crystals (Intermediate 3) were obtained in the same manner as in Synthesis Example 2 (1) except that the change was made to (Intermediate 2) 17.0 g.
As a result of analysis by ¹ H-NMR, it was confirmed that the pale yellow crystals were 1- (3,4-dimethoxy-2-nitrophenyl) -2-methyl-propanone (intermediate 3).

(3) Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol In Synthesis Example 2 (2), “(Intermediate 1) 10.0 g” was replaced with “(Intermediate 3) 12 0.0 g "was obtained in the same manner as in Synthesis Example 2 (2) except that 10.0 g of pale yellow crystals were obtained.
As a result of analysis by ¹ H-NMR, it was confirmed that the pale yellow crystals were 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol.

<Synthesis Example 4>
Synthesis of 1- (2-nitro-4.5-dimethoxyphenyl) -1- (2-nitrophenyl) -methanol A 300 ml three-necked glass flask equipped with a dropping funnel, a thermometer and a magnetic stirrer was purged with nitrogen. , 5-Dimethoxy-2-nitrobenzaldehyde (3.0 g) and tetrahydrofuran (200 ml) were added and dissolved. The solution was added dropwise from a dropping funnel so that the temperature did not exceed 5 ° C., and the solution was stirred at 5 ° C. or lower for 3 hours. Thereafter, 300 ml of a saturated aqueous ammonium chloride solution and 300 ml of diethyl ether were added to the reaction solution, and after stirring for 1 hour, the organic layer was separated. The organic layer was washed with 200 ml of water three times, the organic layer was separated, the solvent was distilled off under reduced pressure with a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 2.0 g of a yellow solid. .
As a result of analysis by ¹ H-NMR, it was confirmed that this yellow solid was 1- (2-nitro-4.5-dimethoxyphenyl) -1- (2-nitrophenyl) -methanol.

<Synthesis Example 5>
Synthesis of 2- (4,5-dimethoxy-2-nitrophenyl) propanol (1) Synthesis of 4,5-dimethoxyethylbenzene (intermediate 4) 500 ml three-neck glass flask equipped with dropping funnel, thermometer and magnetic stirrer Was replaced with nitrogen, charged with 6.68 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.), 5.52 g of 1,2-dimethoxybenzene (Wako Pure Chemical Industries, Ltd.) and 30 ml of dichloromethane, and stirred with a magnetic stirrer. The mixture was cooled in a bath to obtain a mixed solution of 0 to 5 ° C.
On the other hand, 3.0 g of ethyl chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 ml of dichloromethane to obtain a dichloromethane solution of ethyl chloride.

While maintaining the temperature of the previous mixture at 0 to 5 ° C. in an ice bath, the dichloromethane solution was added dropwise to the mixture over 30 minutes from the dropping funnel, and then the ice bath was removed and room temperature (about 25 ° C. ) For 2 hours. Thereafter, 40 ml of 2N hydrochloric acid, 100 ml of water and 100 g of dichloromethane were added to the reaction solution and stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with 200 ml of water three times, the organic layer was separated, the solvent was distilled off under reduced pressure using a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain a yellow oil (intermediate 4). 2.00 g was obtained.
As a result of analysis by ¹ H-NMR, it was confirmed that this yellow oil was 4,5-dimethoxyethylbenzene (intermediate 4).

(2) Synthesis of 2-ethyl-4,5-dimethoxy-nitrobenzene (intermediate 5) In Synthesis Example 2 (1), “4,5-dimethoxyacetophenone 15.0 g” was changed to “(intermediate 4) 10.0 g”. In the same manner as in Synthesis Example 2 (1) except for the change to 8.0, pale yellow crystals (Intermediate 5) 8.0 g were obtained.
As a result of analysis by ¹ H-NMR, it was confirmed that the yellow crystals were 2-ethyl-4,5-dimethoxy-nitrobenzene (intermediate 5).

(3) Synthesis of 2- (4,5-dimethoxy-2-nitrophenyl) propanol A 100 ml two-necked eggplant flask was purged with nitrogen. To this, 3.0 g of (Intermediate 5) and 30 ml of dimethyl sulfoxide were added. After dissolving at about 25 ° C., 1.0 g of paraformaldehyde (Wako Pure Chemical Industries, Ltd.) and 1.0 g of t-butoxypotassium (Wako Pure Chemical Industries, Ltd.) were added, and the mixture was added at room temperature (about 25). Stir for hours. The reaction solution was neutralized with a saturated aqueous solution of sodium bicarbonate, dichloromethane and water were added and stirred for 30 minutes, and then the organic layer was separated. The organic layer was washed with 200 ml of water three times, and the organic layer was separated. The solvent was distilled off under reduced pressure using a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 2.0 g of a yellow solid.
As a result of analysis by ¹ H-NMR, it was confirmed that this yellow solid was 2- (4,5-dimethoxy-2-nitrophenyl) propanol.

<Synthesis Example 6>
Synthesis of N- (3-aminopropyl) -6-heptane lactam In a 100 ml Meyer flask, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, San Apro, Inc., “DBU” (Registered product) 15 g and 10 g of water were added, and the mixture was heated and stirred at 80 ° C. for 2 hours, and then the water was distilled off with a vacuum dryer to obtain 16.5 g of a transparent oily substance.
As a result of analysis by ¹ H-NMR, it was confirmed that this transparent oily substance was N- (3-aminopropyl) -6-heptane lactam.

<Synthesis Example 7>
Synthesis of N- (3-aminopropyl) -4-pentanelactam To a 100 ml Meyer flask, 15 g of 1,5-diazabicyclo [4.3.0] non-5-ene (DBN, San Apro Co., Ltd.) and 10 g of water were added. The mixture was heated and stirred at 80 ° C. for 2 hours, and then water was distilled off with a vacuum dryer to obtain 16.5 g of a transparent oily substance.
As a result of analysis by ¹ H-NMR, it was confirmed that this transparent oil was N- (3-aminopropyl) -4-pentanelactam.

<Synthesis Example 8>
Synthesis of N- (3-aminopropyl) -N-methylacetamide (1) Synthesis of N- (3-aminopropyl) -acetamide (intermediate 6) In a 100 ml Meyer flask, propylenediamine (Wako Pure Chemical Industries, Ltd.) 3.0 g and 1.0 g of methyl acetic acid (Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature (about 25 ° C.) for 3 hours to obtain 4.0 g of a transparent oil.
This transparent oil was purified by silica gel column chromatography to obtain a transparent oil (intermediate 6).
As a result of analysis by ¹ H-NMR, it was confirmed that this transparent oil was N- (3-aminopropyl) -acetamide.

(2) Synthesis of N- (3-aminopropyl) -N-methylacetamide In a 100 ml Meyer flask, 4.0 g of (Intermediate 6) and 2.0 g of bis (1,1-dimethylethyl) dicarbonate (Wako Pure Chemical Industries, Ltd.) ) And stirred at room temperature (about 25 ° C.) for 3 hours to protect the amino group with the Boc group. Thereafter, 1.0 g of dimethyl sulfate (Wako Pure Chemical Industries, Ltd.) was added and stirred for 3 hours at room temperature (about 25 ° C.), then 5.0 g of 2N hydrochloric acid was added, and 1 hour at room temperature (about 25 ° C.). The transparent oily substance which agitated and settled at the bottom of the flask was separated to obtain 4.0 g of a transparent oily substance.
As a result of analysis by ¹ H-NMR, it was confirmed that this transparent oil was N- (3-aminopropyl) -N-methylacetamide.

<Production Example 1> Production of photobase generator (1) Synthesis of N- (N '-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl) aminopropyl) -6-heptanelactam Dropping funnel, thermometer and A 100 ml three-necked glass flask equipped with a magnetic stirrer was purged with nitrogen, and 1.78 g of N, N′-carbonyldiimidazole (Tokyo Chemical Industry Co., Ltd.) and 5 ml of N, N-dimethylformamide were added and suspended. The suspension was cooled with an ice bath while stirring with a magnetic stirrer to obtain a suspension at 0 to 5 ° C.
On the other hand, 2.13 g of “4,5-dimethoxy-2-nitrobenzyl alcohol” obtained in Synthesis Example 1 was dissolved in 5 ml of N, N-dimethylformamide to obtain DMF of 4,5-dimethoxy-2-nitrobenzyl alcohol. A solution was obtained.

  While maintaining the temperature of the suspension at 0 to 5 ° C. in an ice bath, this DMF solution was added dropwise to the suspension over 30 minutes from the dropping funnel, and after aging at 0 to 5 ° C. for 30 minutes, While maintaining the reaction solution at this temperature, a solution of 2.40 g of “N- (aminopropyl) -6-heptanelactam” obtained in Synthesis Example 6 in 5 ml of DMF was added dropwise from a dropping funnel over 10 minutes. It was. Then, after removing the ice bath and aging the reaction solution at room temperature (about 25 ° C.) for 4 hours, the reaction solution is concentrated with a rotary evaporator to remove DMF, and the residue is purified by silica gel column chromatography and used in the present invention. The obtained photobase generator (1) (light yellow solid 3.29 g) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.7 (s, 1H), 7.35 (t, 1H), 7.15 (s, 1H), 5 .30 (s, 2H), 3.85 (d, 6H), 3.4-3.2 (m, 4H), 3.0 (m, 2H), 2.4 (m, 2H), 1. 8-1.3 (m, 8H)}, confirming that this pale yellow solid is N- (N ′-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl) aminopropyl) -6-heptane lactam. did.

<Production Example 2> Production of photobase generator (2) Synthesis of N- (N '-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -6-heptane lactam In Production Example 1, “2.13 g of 4,5-dimethoxy-2-nitrobenzyl alcohol obtained in Synthesis Example 1” was changed to “1- (4,5-dimethoxy-2-nitrophenyl) ethanol 2 obtained in Synthesis Example 2”. .3 g ”, the photobase generator (2) (light yellow solid 3.3 g) used in the present invention was obtained in the same manner as in Production Example 1, except that it was changed to“ 3 g ”.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2.40 (m, 2H), 1. 70-1.40 (m, 11H)}, this pale yellow solid is N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -6-heptane Confirmed to be lactam.

<Production Example 3> Production of photobase generator (3) N- (N '-((1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propoxy) carbonyl) aminopropyl) -6 -Synthesis of heptane lactam In Production Example 1, "2.13 g of 4,5-dimethoxy-2-nitrobenzyl alcohol obtained in Synthesis Example 1" was converted to "1- (4,5-dimethoxy-2- A photobase generator (3) used in the present invention (3.5 g of a pale yellow solid) was obtained in the same manner as in Production Example 1, except that it was changed to 2.6 g of “nitrophenyl) -2-methyl-propanol”. .

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.60 (s, 1H), 7.00 (s, 1H), 6.25 (d, 1H), 6 .10 (t, 1H), 3.90 (d, 6H), 3.40-3.25 (m, 4H), 3.00 (m, 2H), 2.50 (m, 2H), 77-1.50 (m, 8H), 0.90 (t, 6H)}, this pale yellow solid was N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) -2 -Methyl-propoxy) carbonyl) aminopropyl) -6-heptane lactam.

<Production Example 4> Production of photobase generator (4) N- (N '-((1- (4,5-dimethoxy-2-nitrophenyl) -1- (2-nitrophenyl) methoxy) carbonyl) amino Synthesis of Propyl) -6-heptane lactam In Production Example 1, “2.13 g of 4,5-dimethoxy-2-nitrobenzyl alcohol obtained in Synthesis Example 1” was obtained as “1- (2-nitro-) obtained in Synthesis Example 4”. Photobase generator (4) (pale) used in the present invention in the same manner as in Production Example 1 except that it was changed to "3.0 g of 4.5-dimethoxyphenyl) -1- (2-nitrophenyl) -methanol". A yellow solid (4.0 g) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.02 (d, 1H), 7.75 (s, 1H), 7.65 (m, 2H), 7 .60 (s, 1H), 7.48 (t, 1H), 7.22 (d, 1H), 7.00 (s, 1H), 3.85 (d, 6H), 3.40-3. 20 (m, 4H), 2.90 (m, 2H), 2.40 (m, 2H), 1.70-1.40 (m, 8H)}, and this pale yellow solid is N- (N'- ((1- (4,5-dimethoxy-2-nitrophenyl) -1- (2-nitrophenyl) methoxy) carbonyl) aminopropyl) -6-heptane lactam was confirmed.

<Production Example 5> Production of photobase generator (5) Synthesis of N- (N '-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -4-pentanelactam In Production Example 1, “2.13 g of 4,5-dimethoxy-2-nitrobenzyl alcohol obtained in Synthesis Example 1” was changed to “1- (4,5-dimethoxy-2-nitrophenyl) ethanol 2 obtained in Synthesis Example 2”. .3 g ”,“ N- (aminopropyl) -6-heptane lactam 2.40 g obtained in Synthesis Example 6 ”was replaced with“ N- (3-aminopropyl) -4-pentane obtained in Synthesis Example 7 ”. A photobase generator (5) (light yellow solid 4.0 g) used in the present invention was obtained in the same manner as in Production Example 1 except that the amount was changed to “lactam 2.30 g”.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2.40 (m, 2H), 1. 70-1.40 (m, 7H)}, this pale yellow solid is N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -4-pentane. Confirmed to be lactam.

<Production Example 6> Production of photobase generator (6) Synthesis of N- (N '-((2- (4,5-dimethoxy-2-nitrophenyl) propoxy) carbonyl) aminopropyl) -6-heptanelactam In Production Example 1, “2,5-dimethoxy-2-nitrobenzyl alcohol 2.13 g obtained in Synthesis Example 1” was replaced with “2- (4,5-dimethoxy-2-nitrophenyl) propanol 3 obtained in Synthesis Example 5. .2 g ", except that the photobase generator (6) (light yellow solid 4.0 g) used in the present invention was obtained in the same manner as in Production Example 1.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 4.10 (d, 2H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2. 40 (m, 2H), 1.70-1.40 (m, 11H)}, this pale yellow solid is N- (N ′-((2- (4,5-dimethoxy-2-nitrophenyl) propoxy). )) Carbonyl) aminopropyl) -6-heptane lactam.

<Production Example 7> Production of photobase generator (7) Synthesis of N- (N '-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -N-methylacetamide In Production Example 1, “2.13 g of 4,5-dimethoxy-2-nitrobenzyl alcohol obtained in Synthesis Example 1” was changed to “1- (4,5-dimethoxy-2-nitrophenyl) ethanol 2 obtained in Synthesis Example 2”. .3 g ”,“ N- (aminopropyl) -6-heptane lactam obtained in Synthesis Example 6 2.40 g ”was replaced with“ N- (3-aminopropyl) -N-methyl obtained in Synthesis Example 8 ”. A photobase generator (7) (pale yellow solid 3.0 g) used in the present invention was obtained in the same manner as in Production Example 1 except that it was changed to “acetamide 2.00 g”.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2.70 (s, 3H), 2. 00 (s, 3H), 1,60 (d, 3H)}, this pale yellow solid is N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) amino Propyl) -N-methylacetamide was confirmed.

<Production Example 8> Synthesis of Polyimide Precursor A nitrogen-substituted 500 mL four-neck separable flask was charged with 20.0 g (100 mmol) of 4,4′-diaminodiphenyl ether and 200 mL of dehydrated N, N-dimethylacetamide in an ice bath. Stir to dissolve. To this solution, 29.4 g (100 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and stirred for 2 hours in an ice bath. The reaction solution was reprecipitated with acetone, and the precipitate obtained by filtration was dried under reduced pressure at room temperature for 8 hours to quantitatively obtain polyamic acid (polyimide precursor 1) as a white solid.

(Comparative Production Example 1) Synthesis of Comparative Photobase Generator (H1) Synthesis of N- (4,5-dimethoxy-2-nitrobenzyloxycarbonyl) -2,6-dimethylpiperidine In Production Example 1, “Synthesis Example 6” Comparative photobase generator (H1 ) (2.0 g of a pale yellow solid) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.10 (s, 1H), 5.35 (s, 2H), 4 .23 (m, 2H), 3.90 (d, 6H), 1.80-1.60 (m, 1H), 1.50 (m, 4H), 1.40 (m, 1H), 1. 15 (d, 6H)}, and this pale yellow solid was confirmed to be N- (4,5-dimethoxy-2-nitrobenzyloxycarbonyl) -2,6-dimethylpiperidine.

<Test>
(1) the molar extinction coefficient of the measuring photobase generator (1) to (3), and compared photobase generator with (H1), respectively, were weighed using an electronic balance, by using a measuring flask, concentration 10 ^{- A 4} mol / L acetonitrile solution was prepared. This solution was put in a quartz cell (optical path length: 1 cm), and an ultraviolet-visible absorption spectrum in a wavelength range of 190 to 800 nm was measured with a spectrophotometer (UV-2550 manufactured by Shimadzu Corporation). From the absorbance obtained from the spectrum, the molar extinction coefficient was calculated by the following equation. The results are shown in Table 1. It was found that the photobase generators (2) and (3) used in the present invention efficiently absorb light with wavelengths of 365 and 405 nm.

(2) Measurement of optical resolution (2-1)
It was confirmed as follows that the photobase generator of the present invention generates a primary amine when exposed to light, and further generates amidine by heating the primary amine.

2.17 mg of the photobase generator (1) used in the present invention and 0.75 g of heavy DMSO (DMSO-d6) were uniformly dissolved (concentration 7.02 × 10 ⁻⁶ mol / L) and filled in an NMR tube. Then, exposure (50 J / cm ² with an integrated light amount of 365 nm) was performed with a belt conveyor type UV irradiation apparatus (Eye Graphics Co., ECS-151U). In addition, in order to control an exposure wavelength, the filter (Eye Graphics Co., Ltd. 365 filter) which permeate | transmits the light of a wavelength of 300-450 nm was used.
Thereafter, ¹ H-NMR (300 MHz) analysis was performed, and the photobase generator (1) used in the present invention was decomposed to produce a primary amine {N- (aminopropyl) -6-heptanelactam}. {The signal of proton at the benzyl position disappeared 5.30 ppm (s, 2H), and the signal of N- (aminopropyl) -6-heptane lactam was confirmed. }.

  As for the photobase generators (2) to (7) used in the present invention, it was confirmed in the same manner as above that the photobase generators (2) to (7) were decomposed to produce primary amines. {Photobase generators (2) to (5) and (7); The signal of the proton at the benzyl position disappeared, and the signal of the primary amine was confirmed. It was confirmed that the photobase generator (6): 6.10 ppm (q, 1 H) of the proton at the benzyl position was shifted to a high magnetic field of 6.50 ppm (m, 1 H). }

A primary amine (NMR tube) obtained by subjecting the photobase generators (1) to (7) of the present invention to exposure decomposition was heated in an oil bath at 120 ° C. for 1 hour, and then again ¹ H-NMR (300 MHz). ) Analysis, the primary amine signal disappeared and the amidine signal was confirmed. The NMR data of the obtained amidine are shown below.

[Base generators (1), (2), (3), (4), (6)]
NMR data: 3.30 (m, 4H), 3.20 (t, 2H), 2.40 (t, 2H), 1.50-1.80 (m, 8H)
Amidine: 1,8-diazabicyclo [5.4.0] undec-7-ene [base generator (5)]
NMR data: 3.50 (m, 4H), 3.40 (t, 2H), 2.60 (t, 2H), 1.50-1.80 (m, 4H)
Amidine: 1,5-diazabicyclo [4.3.0] non-5-ene [base generator (7)]
NMR data: 3.30 (t, 2H), 2.70 (s, 3H), 1.90 (s, 3H), 1.60 (m, 2H), 1.00 (t, 2H)
Amidine: N-methyl-2-methyl-1,3-diazacyclo-2-ene

Furthermore, the primary amine (NMR tube) obtained by exposing and decomposing the photobase generators (1) to (7) of the present invention is heated in an oil bath at 80, 115, or 150 ° C. for 1 hour. Then, ¹ H-NMR (300 MHz) analysis was performed again, and the conversion rate (mol%) of primary amine to amidine was determined and shown in Table 2.
The conversion rate (mol%) of primary amine to amidine was calculated from the integral value of protons of primary amine and amidine.

(2-2)
About the photobase generators (1) to (3) and the comparative photobase generator (H1), 1.0 mg was weighed into a quartz NMR tube using an electronic balance, and 0.5 mL of heavy acetonitrile was added and dissolved. . Through this filter, all the wavelengths of a high-pressure mercury lamp (SPOT CURE SP-III 250UA manufactured by USHIO INC., Lamp model number: USH-255BY) are passed through the filter 1 that does not transmit a wavelength of 350 nm or less before the filter passes through 100 J / cm ² (i Line conversion: UV illuminance meter: UIT-150 manufactured by Ushio Electric Co., Ltd., light receiver: UVD-S365), 18.2 J / cm ² after passing through the filter (i-line conversion: UV illuminance meter: UIT-150 manufactured by Ushio Electric Co., Ltd., light reception) Apparatus: UVD-S365) The photodegradability was evaluated in a wavelength region of i (365 nm) or longer by irradiating light and comparing NMR spectra before and after irradiation. Similarly, the total wavelength of the high-pressure mercury lamp is 100 J / cm ² before passing through the filter 2 through the filter 2 that does not transmit the wavelength of 380 nm or less (i-line conversion: ultraviolet illuminance meter: UIT-150 manufactured by Ushio Electric Co., photoreceiver: UVD- S365), 470 J / cm ² (h line conversion: UV illuminance meter: UIT-101 manufactured by Ushio Electric Co., Ltd., light receiver: UVD-405PD), 0 J / cm ² after passing through the filter (i line conversion: UV illuminance meter: Ushio Electric) Company UIT-150, light receiver: UVD-S365), 160 J / cm ² (h-line conversion: UV illuminance meter: Ushio Electric Corporation UIT-101, light receiver: UVD-405PD) before and after irradiation By comparing the NMR spectra, the photodegradability in the wavelength region of h line (405 nm) or more was evaluated. FIG. 1 shows transmittance curves of the filter 1 and the filter 2. Table 3 shows the evaluation results of the photodegradability.

  It has been clarified that the photobase generators (2) and (3) are photodegradable in the wavelength region of i-line and h-line. The photobase generator (1) was found to have i-line sensitivity comparable to that of the comparative photobase generator (H1), although h-line is not photodegradable.

(3) Measurement of thermal stability The photobase generators (1) to (3) and the comparative photobase generator (H1) were heated from 30 ° C. to 600 ° C. using DTG-60 (manufactured by Shimadzu Corporation). TG-DTA measurement was performed at a rate of 10 ° C./min. The 5% weight loss temperature was calculated and the heat resistance was evaluated. Table 4 shows the evaluation results of heat resistance.

Example 1
0.12 g of the photobase generator (1), 1 g of the polyimide precursor 1 and 8.2 g of N, N-dimethylacetamide were dissolved, and the photosensitive resin composition (photosensitive resin composition 1) of the present invention was dissolved. Obtained.

(Example 2)
0.12 g of the photobase generator (2), 1 g of the polyimide precursor 1 and 8.2 g of N, N-dimethylacetamide were dissolved, and the photosensitive resin composition (photosensitive resin composition 2) of the present invention was dissolved. Obtained.

(Example 3)
0.12 g of the photobase generator (3), 1 g of the polyimide precursor 1 and 8.2 g of N, N-dimethylacetamide were dissolved, and the photosensitive resin composition (photosensitive resin composition 3) of the present invention was dissolved. Obtained.

Example 4
0.12 g of the photobase generator (4), 1 g of the polyimide precursor 1 and 8.2 g of N, N-dimethylacetamide were dissolved, and the photosensitive resin composition (photosensitive resin composition 4) of the present invention was dissolved. Obtained.

(Comparative Example 1)
0.12 g of the comparative photobase generator (H1), 1 g of the polyimide precursor 1 and 8.2 g of N, N-dimethylacetamide were dissolved to obtain a photosensitive resin composition (Comparative photosensitive resin composition 1). It was.
(Comparative Example 2)
0.15 g of the comparative photobase generator (H1), 1 g of the polyimide precursor 1 and 8.2 g of N, N-dimethylacetamide were dissolved to obtain a photosensitive resin composition (Comparative photosensitive resin composition 1). It was.

[Evaluation]
(1) Imidization promoting effect of amine A polyimide precursor varnish was prepared by dissolving the polyimide precursor 1 in 1 g and 8.2 g of N, N-dimethylacetamide. Four resin compositions were prepared by adding 1, 3, 5, or 7 wt% of diazabicycloundecene to the solid content of the polyimide precursor 1 in the prepared varnish. Each resin composition was spin-coated on a chrome-plated glass plate to a film thickness of 4 μm, dried on a hot plate at 100 ° C. for 10 minutes, and then heated at 180 ° C. for 10 minutes. The imidation ratio of each sample was measured by measuring the IR spectrum of each coating film. Moreover, the sample was similarly produced about the resin composition which added 1, 3, 5, 7 wt% of cyclohexylamine with respect to solid content of the polyimide precursor 1, IR spectrum was measured, and the comparison was performed.

  The result is as shown in FIG. It was revealed that diazabicycloundecene has a high effect of promoting imidization reaction even with a small addition amount as compared with cyclohexylamine.

(2) Pattern formation The photosensitive resin composition 1 was spin-coated on a glass plate so as to have a final film thickness of 4 μm, and dried on a hot plate at 100 ° C. for 10 minutes. Then, after performing ultraviolet-visible light irradiation of ² J / cm ^{2 in} terms of i-line with a manual exposure device (manufactured by Dainippon Kaken, MA-1100), and then heating on a hot plate at 170 ° C. for 5 minutes, Tetramethylammonium hydroxide was immersed in a solution obtained by adding 10 wt% of isopropanol to a 2.38% solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 300 ° C. for 1 hour to perform imidization.
The photosensitive resin composition 2 was spin-coated on a glass plate so as to have a final film thickness of 2 μm, and dried on a hot plate at 100 ° C. for 10 minutes. Then, 1 J / cm ² of ultraviolet-visible light irradiation was performed in a manual exposure apparatus (manufactured by Dainippon Kaken, MA-1100) in terms of i-line, and then heated on a hot plate at 170 ° C. for 5 minutes. Tetramethylammonium hydroxide was immersed in a solution obtained by adding 10 wt% of isopropanol to a 2.38% solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 300 ° C. for 1 hour to perform imidization.
The photosensitive resin composition 3 was spin-coated on a glass plate so as to have a final film thickness of 2 μm, and dried on a hot plate at 100 ° C. for 10 minutes. Then, 1 J / cm ² of ultraviolet-visible light irradiation was performed in a manual exposure apparatus (manufactured by Dainippon Kaken, MA-1100) in terms of i-line, and then heated on a hot plate at 170 ° C. for 5 minutes. Tetramethylammonium hydroxide was immersed in a solution obtained by adding 10 wt% of isopropanol to a 2.38% solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 300 ° C. for 1 hour to perform imidization.
The photosensitive resin composition 4 was spin-coated on a glass plate so as to have a final film thickness of 5 μm, and dried on a hot plate at 100 ° C. for 10 minutes. Then, 1 J / cm ² of ultraviolet-visible light irradiation was performed in a manual exposure apparatus (manufactured by Dainippon Kaken, MA-1100) in terms of i-line, and then heated on a hot plate at 170 ° C. for 5 minutes. Tetramethylammonium hydroxide was immersed in a solution obtained by adding 10 wt% of isopropanol to a 2.38% solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 300 ° C. for 1 hour to perform imidization.
From this result, it became clear that the photosensitive resin composition of the present invention can form a good pattern.
Similarly, pattern formation was performed using the comparative photosensitive resin composition 1, but the pattern film did not remain even in the exposed portion, and a pattern could not be obtained. When pattern formation was performed using the comparative photosensitive resin composition 2 in which the addition amount of the photobase generator was increased, it was possible to form a pattern by irradiation at ² J / cm ² .

Claims (14)

The photosensitive resin composition containing the photobase generator represented by General formula (1) or General formula (2), and a polyimide precursor.

(R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is (An integer of 2-3, m is an integer of 3-5, A is group represented by General formula (3) or General formula (4).)

(R ³ is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, A group consisting of an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, and a halogen atom Represents a phenyl group having at least one substituent selected from R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 carbon atoms. Represents an aryl group having 12 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, or a halogen atom; 4 adjustments , When q is 2 to 4, ^{R 4} may be the same or different.) The photosensitive resin composition of Claim 1 whose said photobase generator is a photobase generator represented by General formula (2-1) or General formula (2-2).

(A is a group represented by the general formula (3) or the general formula (4).) In the photobase generator, A in the general formula (1), the general formula (2), the general formula (2-1), or the general formula (2-2) is represented by the formulas (3-1) to (3-4). The photosensitive resin composition in any one of Claims 1 thru | or 2 which is group represented by either of these, or group represented by either of Formula (4-1)-(4-3).

  The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyimide precursor itself is one that promotes a reaction to a final product by the action of a basic substance.   The photosensitive material according to claim 1, wherein the polyimide precursor itself is a substance whose reaction to the final product is promoted by the action of a basic substance and whose solubility is changed by heating. Resin composition.   Furthermore, the photosensitive resin composition in any one of the Claims 1 thru | or 5 containing a sensitizer.   The photosensitive resin composition according to claim 1, wherein the polyimide precursor is a polyamic acid.   The photosensitive resin composition according to claim 1, wherein the photobase generator has photodegradability with respect to electromagnetic waves having a wavelength of 350 nm or more.   The photosensitive resin composition in any one of Claims 1 thru | or 8 in which the said photobase generator has photodegradability with respect to the electromagnetic waves with a wavelength of 400 nm or more.   The photosensitive resin composition in any one of Claims 1 thru | or 9 whose 5% weight reduction | decrease temperature of the said photobase generator is 170 degreeC or more.   Paint or printing ink, or color filter, flexible display film, semiconductor device, electronic component, interlayer insulation film, wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material The photosensitive resin composition in any one of Claims 1 thru | or 10 used as a material.   A printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, at least a part of which is formed of the photosensitive resin composition according to claim 1 or a cured product thereof. Article of any of wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material.   The surface of the coating film or molded body comprising the photosensitive resin composition according to any one of claims 1 to 11 is irradiated with electromagnetic waves in a predetermined pattern, and the electromagnetic wave irradiation site of the coating film or molded body is dissolved. A negative pattern forming method in which development is performed after selectively reducing the properties.   The negative pattern formation method of Claim 13 which performs heat processing after irradiating electromagnetic waves, and selectively reduces the solubility of the electromagnetic wave irradiation site | part of the said coating film or a molded object.

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