Polyimide resin and its manufacturing method, photosensitive resin composition, pattern forming method and cured film forming method, interlayer insulating film, surface protective film, electronic components

Abstract

To provide: a compound allowing derivation of a polyimide that can be used as a base resin for a photosensitive resin composition which can form a fine pattern and can achieve high resolution without impairing excellent properties such as mechanical strength and solubility; a polyimide resin obtained using the compound; and a method of producing the same.SOLUTION: The compound is represented by the general formula (1) in the figure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound useful as a structural unit of a polyimide resin, a polyimide resin obtained by using the compound and a method for producing the same, a positive-type photosensitive resin composition or a negative-type photosensitive resin composition using the polyimide resin as a base resin, a pattern forming method using the composition and the composition that allows development with an alkaline aqueous solution, and a method for forming a cured film.The present invention also relates to an interlayer insulating film, a surface protective film, and an electronic component using the cured film. [Background technology]

[0002] As various electronic devices such as personal computers, digital cameras, and mobile phones become smaller and more powerful, there is a rapidly growing demand for semiconductor elements to be smaller, thinner, and more dense. For this reason, there is a demand for the development of photosensitive insulating materials that can accommodate the increase in substrate area required for improved productivity and that can be finely patterned on substrates with high aspect ratios in high-density packaging technologies such as chip-size packages (CSPs) and three-dimensional stacking.

[0003] In high-density packaging technologies such as three-dimensional stacking, polyimide-based materials and polybenzoxazole-based materials have long been used as protective coatings or insulating layers as photosensitive insulating materials that can be patterned on substrates. Their excellent mechanical properties, such as insulation, heat resistance, high elongation and high strength, as well as adhesion to substrates, have attracted attention, and their development is still active today.

[0004] Conventionally, photosensitive polyimide-based materials have been proposed that utilize polyamic acid, which is a precursor of polyimide, such as a material in which a photosensitive group is introduced into the carboxyl group of polyamic acid via an ester bond (Patent Document 1, Patent Document 2). In these proposals, after forming a patterned film, an imidization treatment at a high temperature exceeding 300°C is essential to obtain the desired polyimide film.

[0005] However, in recent years, due to demands for reducing the thermal load on devices and reducing stress on substrates, there is a demand for polyimide-based or polybenzoxazole-based materials that can be cured at low temperatures of 250° C. or less, more preferably 200° C. or less.

[0006] As a low-temperature curable resin composition, a photosensitive polyimide resin composition using a solvent-soluble resin that has already been imidized has been proposed (Patent Document 3). The negative-type photosensitive resin composition using polyimide described in Patent Document 3 is developed using N-methyl-2-pyrrolidone (NMP) in pattern formation, but Patent Document 3 does not specifically describe the resolution performance in pattern formation.

[0007] As polyimide materials having excellent mechanical properties such as heat resistance and tensile strength, various materials containing aromatic substituents having a rigid planar structure in the resin structure are known (Patent Document 4). These materials have a very high glass transition point, almost no weight loss under high temperature conditions, and excellent tensile strength, and are therefore widely used in various heat-resistant, wear-resistant, and insulating material applications. On the other hand, such polyimide resins have poor solubility in organic solvents, and require amide-based solvents such as NMP, which have excellent dissolving power, as a solvent for coating and forming. However, such solvents have become the subject of environmental regulations in recent years due to their high toxicity, and it is desirable to replace them with solvents with lower toxicity.

[0008] Furthermore, when such a substituent is applied to a lithography material, the solubility of the polyimide resin in an alkaline aqueous solution is significantly reduced, which may significantly impair the lithography performance, particularly in positive tone lithography. Also, in negative tone lithography, the lithography performance is inevitably impaired due to the low solubility in organic solvents.

[0009] For these reasons, in order to introduce rigid aromatic substituents into lithopatternable polyimide materials and improve their mechanical properties, it is essential to design them to ensure solubility in organic solvents and alkaline aqueous solutions.

[0010] As a polyimide material with improved organic solvent solubility, one that has introduced a 9,9-diphenylfluorene skeleton is known (Patent Document 5). Although the 9,9-diphenylfluorene skeleton has a highly planar fluorene structure, it is said to exhibit good solubility in organic solvents despite its high aromatic ring density due to its characteristic of orienting substituents perpendicular to the conjugated plane (cardo structure), and this document evaluates the performance using γ-butyrolactone alone as the solvent during coating formation. On the other hand, although γ-butyrolactone has high dissolving power, it is known that it is prone to coating failure due to its high surface tension, and the above document does not provide sufficient description of the solubility of polyimide resins in propylene glycol monomethyl ether acetate (PGMEA), which has poorer dissolving power than γ-butyrolactone but is more desirable from the viewpoint of coating.

[0011] Furthermore, polyimide resins having a 1,1-diphenylcyclohexane structure as a structural unit containing a cardo structure are also known (Patent Document 6). This structural unit has an alicyclic structure that has a low aromatic density and excellent solubility compared to the above-mentioned fluorene structure, so it is expected to have higher solvent solubility, but on the other hand, it is known that it has inferior heat resistance and mechanical strength compared to polyimide resins with high aromatic density.

[0012] As described above, in the future, as chips become increasingly dense and highly integrated, it is expected that patterns in the rewiring technology for insulating protective films will become increasingly finer. Therefore, there is a strong demand for photosensitive resin compositions using polyimide resins that can realize high resolution without impairing the excellent mechanical properties, particularly strength, and further adhesion, of the polyimide patterns and protective coatings obtained by heating.

[0013] It is also highly desirable for the insulating protective film that has been patterned and cured to have heat resistance in the various processes and resistance to the various chemicals used.

[0014] That is, there is a need for the rapid development of a photosensitive resin composition which has all of these characteristics without lacking any one of them. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] Japanese Unexamined Patent Publication No. 115541 / 1983 [Patent Document 2] Japanese Patent Application Publication No. 55-45746 [Patent Document 3] Patent No. 3232022 [Patent Document 4] Patent No. 5233344 [Patent Document 5] International Publication No. 2019 / 151336 [Patent Document 6] JP 2019-14828 A Summary of the Invention [Problem to be solved by the invention]

[0016] The present invention has been made in view of the above circumstances, and has an object to provide a compound capable of deriving a polyimide that can be used as a base resin for a photosensitive resin composition capable of forming a fine pattern and obtaining high resolution without impairing excellent characteristics such as mechanical strength and elongation, a polyimide resin obtained by using the compound, and a method for producing the same. Another object of the present invention is to provide a positive-type photosensitive resin composition and a negative-type photosensitive resin composition using the polyimide resin that is soluble in an alkaline aqueous solution, has excellent resolution, and is capable of forming a fine pattern in pattern formation. [Means for solving the problem]

[0017] In order to solve the above problems, the present invention provides a compound represented by the following general formula (1): [ka] (In the formula, Z represents a linear, branched or cyclic divalent hydrocarbon group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. X 1 ~X 3 HA-CO 2 -,-CONR X1 -, -O-, -NR X1 -, -S-, -SO 2 -, -SO 3 -, -SO 2 NR X1 -, which may be the same or different. However, R X1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. Ar is a divalent aromatic group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L 1 ~L 2 each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. x and y each independently represent 0 or 1.

[0018] Such a compound can lead to a polyimide that can be used as a base resin for a photosensitive resin composition capable of forming a pattern without impairing excellent characteristics such as mechanical strength and elongation.

[0019] In this case, X in general formula (1) 3 Ga-CO 2 -, -NR X1 It can be either - or -O-.

[0020] Such an X 3 is a condensation linking group frequently used in general-purpose polycondensation polymers and is therefore desirable.

[0021] In addition, from the viewpoints of ease of synthesis and availability of raw materials, it is desirable that x and y in the general formula (1) are 0.

[0022] The present invention also provides a resin characterized by containing structural units represented by the following general formulas (2) and (3): [ka] (In the formula, Z represents a linear, branched or cyclic divalent hydrocarbon group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. X 1 ~X 3 HA-CO 2 -,-CONR X1 -, -O-, -NR X1 -, -S-, -SO 2 -, -SO 3 -, -SO 2 NR X1 -, which may be the same or different. However, R X1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. Ar is a divalent aromatic group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L 1 ~L 2 each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. x and y each independently represent 0 or 1. Y 1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0023] Such a resin can be used as a base resin for a photosensitive resin composition capable of forming a pattern without impairing excellent characteristics such as mechanical strength and elongation.

[0024] In this case, it is preferable that the structural unit represented by the following general formula (4) is further contained in addition to the structural units (2) and (3). [ka] (In the formula, L 3 is a single bond or a divalent linking group, R 1 ~R2 Each of w and z independently represents an arbitrary monovalent substituent. When w and z are 2 or more, multiple R 1 and R 2 The substituents represented by may be the same or different.

[0025] A resin containing such a structural unit is soluble in a basic aqueous solution and a basic organic solvent due to the effect of the acidic hydroxy group of the phenol unit. Therefore, the water solubility and organic solvent solubility can be controlled by adding a photosensitive or radiation sensitive additive and a solubility control agent, and as a result, patterning by lithography can be performed favorably.

[0026] In this case, L in the general formula (4) 3 -CR f1 R f2 -OR-SO 2 -, where R f1 ~R f2 are preferably each independently a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

[0027] Such resins have higher solubility in basic aqueous solutions and basic organic solvents due to the high acidity of the phenolic hydroxyl groups, making them suitable for use in lithography.

[0028] The present invention also provides a method for producing the above-mentioned resin, which comprises reacting (i) the above-mentioned compound or an acid halide or an acid anhydride derived therefrom with (ii) the compound represented by the following general formula (5), and (iii) at least one of the compounds represented by the following general formulas (6) to (7). [ka] (In the formula, Y 1 is the same as above. Y 2 X represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. 4is a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCO 2 R X4 , -OSO 2 R X4 , -OSO 3 R X4 However, R X4 is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0029] Such a method for producing a resin makes it possible to suitably produce a base resin for a photosensitive resin composition that can be patterned without impairing excellent characteristics such as mechanical strength and elongation.

[0030] The present invention also provides a positive photosensitive resin composition comprising: (A) the above resin; (B) a photosensitizer that generates an acid when exposed to light and has an increased dissolution rate in an alkaline aqueous solution, the photosensitizer being a compound having a quinone diazide structure; and (D) a solvent.

[0031] In addition to the above, the present invention further provides a positive photosensitive resin composition comprising (C) one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'). [ka] (In the formula, the dotted line represents a bond, and R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.

[0032] In the case of such a positive-type photosensitive resin composition, by using a photosensitizer as component (B), in pattern formation, the exposed areas become soluble in an alkaline aqueous developer due to a high dissolution rate, while the unexposed areas do not dissolve because the photosensitizer prevents alkali dissolution, and therefore a suitable positive image can be obtained.

[0033] The present invention also provides a negative photosensitive resin composition comprising (A') the above resin, (B') a photoacid generator, (C') an amino condensate modified with formaldehyde or a formaldehyde-alcohol, one or more crosslinking agents selected from the group consisting of a phenol compound having two or more methylol groups or alkoxymethylol groups on average per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'), and (D) a solvent. [ka] (In the formula, the dotted line represents a bond, and R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.

[0034] Such a negative-type photosensitive resin composition can provide a suitable negative image in pattern formation by using a photoacid generator as the component (B').

[0035] The present invention also provides a method for producing a semiconductor device comprising the steps of: (1) applying the positive photosensitive resin composition onto a substrate to form a photosensitive film; (2) heating the photosensitive film; (3) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (4) developing with an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of:

[0036] In this way, the positive photosensitive resin composition of the present invention can be subjected to alkaline development using an aqueous alkaline solution.

[0037] The present invention also provides a method for producing a semiconductor device comprising the steps of: (I) applying the negative photosensitive resin composition onto a substrate to form a photosensitive film; (II) heating the photosensitive film; (III) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (IV) developing with an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of:

[0038] In this way, the negative photosensitive resin composition of the present invention also allows alkaline development using an alkaline aqueous solution.

[0039] In this case, it is preferable to include a post-exposure baking step between step (III) and step (IV).

[0040] In this manner, by including a step of heating after exposure (post-exposure bake (PEB)), the crosslinking reaction between the crosslinking agent and the polymer can be promoted.

[0041] The present invention also provides a method for forming a cured coating, comprising the step of post-curing the patterned coating obtained by the above-mentioned pattern formation method by heating at a temperature of 100 to 300°C.

[0042] The method for forming a cured coating of the present invention can increase the crosslink density of a coating of a photosensitive resin composition, remove remaining volatile components, and provide favorable adhesion to substrates, heat resistance, strength, and electrical properties.

[0043] The present invention also provides an interlayer insulating film comprising a cured film obtained by curing the above positive-type photosensitive resin composition or the above negative-type photosensitive resin composition.

[0044] The interlayer insulating film of the present invention has excellent insulating properties, exhibits excellent adhesion, and has mechanical strength suitable for a protective coating, while also achieving significant improvement in resolution performance to enable the formation of finer patterns.

[0045] The present invention also provides a surface protective film comprising a cured coating formed by curing the above positive-type photosensitive resin composition or the above negative-type photosensitive resin composition.

[0046] Such a surface protective film of the present invention is excellent in adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and the like.

[0047] The present invention also provides an electronic component comprising the above interlayer insulating film or the above surface protective film.

[0048] Such an electronic component of the present invention has excellent reliability because it has the interlayer insulating film or the surface protective film. Effect of the Invention

[0049] As described above, the compound of the present invention can lead to a polyimide that can be used as a base resin for a photosensitive resin composition capable of forming a fine pattern and obtaining high resolution without impairing excellent characteristics such as mechanical strength, elongation, etc. Furthermore, the polyimide resin obtained by using the compound can provide a positive-type photosensitive resin composition and a negative-type photosensitive resin composition that are soluble in an alkaline aqueous solution, have excellent resolution, and are capable of forming a fine pattern in pattern formation.

[0050] In particular, the compound of the present invention has a mother skeleton having a cyclic structure, a condensed linking group extending from it in a cardo form, and an aromatic substituent having a condensed linking group, and by using it as a raw material for various polycondensation polymers, it is possible to improve Tg and tensile strength due to the tertiary condensed linking group with a low degree of freedom of structural deformation, and to improve tensile strength and elongation due to the stacking interaction of the aromatic linking group. Furthermore, due to the organic solvent solubility promoting effect of the cardo structure, it has high solubility in various organic solvents.

[0051] Furthermore, a cured coating film obtained from the positive-type photosensitive resin composition or the negative-type photosensitive resin composition of the present invention becomes a protective coating film having excellent mechanical strength, substrate adhesion, electrical properties, reliability, and solvent solubility due to the structure derived from the compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0052] As described above, there has been a demand for the development of a polyimide resin that can be used as a base resin for a pattern-forming photosensitive resin composition without impairing its excellent characteristics such as mechanical strength and elongation.

[0053] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above object, and as a result have found that, when a polyimide resin obtained by using a compound represented by the following general formula (1) is used as a base resin for a photosensitive resin composition, such a polyimide resin is soluble in an alkaline aqueous solution developer and can therefore be used for both a positive-type photosensitive resin composition which can be developed with an alkaline aqueous solution and a negative-type photosensitive resin composition which can be developed with an alkaline aqueous solution, and that patterns obtained by using these photosensitive resin compositions have excellent mechanical strength, elongation, etc.

[0054] Furthermore, it was found that a protective film obtained by forming a pattern and heating using a photosensitive resin composition containing the above polyimide resin as a base resin has excellent electrical properties, mechanical properties, and adhesion. That is, it was found that a cured film having a pattern formed using a photosensitive resin composition containing the above polyimide resin as a base resin is excellent as a protective film for electrical and electronic components and an insulating protective film, and the present invention was completed. In this specification, electrical and electronic components are also collectively referred to as "electronic components".

[0055] That is, the present invention relates to a compound represented by the below-mentioned general formula (1) and a resin containing this compound as a structural unit.

[0056] The present invention will be described in detail below, but the present invention is not limited thereto.

[0057] The present invention provides a compound represented by the following general formula (1): [ka] (In the formula, Z represents a linear, branched or cyclic divalent hydrocarbon group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. X 1 ~X 3 HA-CO 2 -,-CONR X1 -, -O-, -NR X1 -, -S-, -SO 2 -, -SO 3 -, -SO 2 NR X1 -, which may be the same or different. However, R X1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. Ar is a divalent aromatic group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L 1 ~L 2each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. x and y each independently represent 0 or 1.

[0058] In formula (1), Z represents a linear, branched or cyclic divalent hydrocarbon group having 2 to 30 carbon atoms which may be substituted with or interrupted by a heteroatom.

[0059] The divalent hydrocarbon group represented by Z may be linear, branched, or cyclic. Specific examples thereof include an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a tetradecane-1,15-diyl group, a tetradecane-1,16-diyl group, a tetradecane-1,17-diyl group, a tetradecane-1,18-diyl group, a tetradecane-1,19-diyl group, a tetradecane-1,20-diyl group, a tetradecane-1,21-diyl group, a tetradecane-1,22-diyl group, a tetradecane-1,23-diyl group, a tetradecane-1,24-diyl group, a tetradecane-1,25-diyl group, a tetradecane-1,26-diyl group, a tetradecane-1,27-diyl group, a tetradecane-1,28-diyl group, a tetradecane-1,30-diyl group, a tetradecane-1,31-diyl group, a tetradecane-1,32-diyl group, a tetradecane-1,33-diyl group, a tetradecane-1,34-diyl group, a Straight-chain or branched, saturated or unsaturated hydrocarbon groups such as toradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, vinylene group, propene-1,2-diyl group, and propene-1,3-diyl group; cyclopropane-1,2-diyl group, cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane- 1,2-diyl group, cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,2-diyl group, cyclooctane-1,3-diyl group, cyclooctane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,2-diyl group, cyclononane-1,3-diyl group, cyclononane-1,4-diyl group, cyclononane-1,5-diyl group, cyclodecane-1,2-diyl group, cyclodecane-1,3-diyl group, cyclodecane-1,4-diyl group, cyclodecane-1,5-diyl group, cyclodecane-1, saturated or unsaturated cyclic hydrocarbon groups such as norbornane-1,2-diyl, norbornane-1,3-diyl, norbornane-1,4-diyl, norbornane-2,3-diyl, norbornane-2,5-diyl, norbornane-2,6-diyl, norbornane-2,7-diyl, benzene-1,2-diyl, naphthalene-1,2-diyl, biphenyl-2,2'-diyl, cyclopentene-1,2-diyl, cyclohexene-1,2-diyl, cycloheptene-1,2-diyl, and cyclooctene-1,2-diyl;Examples of the divalent substituent include a divalent substituent formed by bonding any two or more of the above-mentioned straight-chain, branched or cyclic hydrocarbon groups and methylene groups; and divalent gem-hydrocarbon groups such as ethane-1,1-diyl group, propane-1,1-diyl group, butane-1,1-diyl group, pentane-1,1-diyl group, hexane-1,1-diyl group, heptane-1,1-diyl group, octane-1,1-diyl group, nonane-1,1-diyl group, decane-1,1-diyl group, cyclopropane-1,1-diyl group, cyclobutane-1,1-diyl group, cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, cycloheptane-1,1-diyl group, cyclooctane-1,1-diyl group, vinylidene group and propene-1,1-diyl group;

[0060] Furthermore, the divalent hydrocarbon group may have some or all of its hydrogen atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and as a result may contain a hydroxy group, an amino group, a cyano group, a nitro group, a haloalkyl group, etc.

[0061] In addition, the divalent hydrocarbon group may have some of its carbon atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, may contain an ether bond, a sulfide bond, a carbonyl group, an ester bond, -N(R)- (wherein R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom), an amide bond, an imino bond, a sulfonyl group, a sulfinyl group, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a carbamate bond, a carboxylic anhydride (-C(=O)-OC(=O)-), or the like.

[0062] The monovalent hydrocarbon group represented by R may be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl, alkenyl groups such as vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl, alkynyl groups such as ethynyl, butynyl, 2-cyclohexylethynyl, and 2-phenylethynyl, aryl groups such as phenyl, naphthyl, and thienyl, aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl, and aracyl groups such as benzoylmethyl and 1-benzoylethyl.

[0063] Furthermore, the monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and as a result may contain a hydroxy group, an amino group, a cyano group, a nitro group, a haloalkyl group, or the like.

[0064] In addition, the monovalent hydrocarbon group may have some of its carbon atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, may contain an ether bond, a sulfide bond, a carbonyl group, an ester bond, -N(R)- (wherein R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom), an amide bond, an imino bond, a sulfonyl group, a sulfinyl group, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a carbamate bond, a carboxylic acid anhydride (-C(=O)-OC(=O)-), or the like.

[0065] In formula (1), the following are particularly suitable as the substituent represented by Z. Here, -* represents a bond. However, the present invention is not limited to these. [ka]

[0066] In formula (1), X 1 ~X 3 HA-CO 2 -,-CONR X1 -, -O-, -NR X1 -, -S-, -SO 2 -, -SO 3 -, -SO 2 NR X1 -, which may be the same or different. X1 represents a monovalent hydrocarbon group which may be substituted with a hydrogen atom or the same heteroatoms as those mentioned above and which may be interrupted by a heteroatom, and has 1 to 30 carbon atoms.

[0067] In formula (1), Ar represents a divalent aromatic group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interposed by a heteroatom. Specific examples thereof include an o-phenylene group, an m-phenylene group, a p-phenylene group, an o-naphthylene group, an m-naphthylene group, a p-naphthylene group, an ana-naphthylene group, an epi-naphthylene group, a kata-naphthylene group, a peri-naphthylene group, a pros-naphthylene group, an amphi-naphthylene group, and a naphthalene-2,7-diyl group.

[0068] Furthermore, the divalent aromatic group may have some or all of its hydrogen atoms substituted with the same monovalent hydrocarbon groups as above.

[0069] Furthermore, the divalent aromatic group may have some or all of its hydrogen atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and as a result may contain a hydroxy group, an amino group, a cyano group, a nitro group, a haloalkyl group, or the like.

[0070] In addition, the divalent aromatic group may have some of its carbon atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, may contain an ether bond, a sulfide bond, a carbonyl group, an ester bond, -N(R)- (wherein R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom), an amide bond, an imino bond, a sulfonyl group, a sulfinyl group, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a carbamate bond, a carboxylic anhydride (-C(=O)-OC(=O)-), or the like.

[0071] In formula (1), the following are particularly suitable as the substituent represented by Ar. Here, -* represents a bond. However, the present invention is not limited to these. [ka]

[0072] In formula (1), L 1 ~L 2 each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. x and y each independently represent 0 or 1. Specifically, examples of the alkylene alkyl group include ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, and the like. linear or branched, saturated or unsaturated hydrocarbon groups such as cyclopropane-1,2-diyl group, cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane-1,2-diyl group, cycloheptane-1, 3-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,2-diyl group, cyclooctane-1,3-diyl group, cyclooctane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,2-diyl group, cyclononane-1,3-diyl group, cyclononane-1,4-diyl group, cyclononane-1,5-diyl group, cyclodecane-1,2-diyl group, cyclodecane-1,3-diyl group, cyclodecane-1,4-diyl group, cyclodecane-1,5-diyl group, cyclodecane-1,6-diyl group, norbornane saturated or unsaturated cyclic hydrocarbon groups such as norbornane-1,2-diyl group, norbornane-1,3-diyl group, norbornane-1,4-diyl group, norbornane-2,3-diyl group, norbornane-2,5-diyl group, norbornane-2,6-diyl group, norbornane-2,7-diyl group, benzene-1,2-diyl group, naphthalene-1,2-diyl group, biphenyl-2,2'-diyl group, cyclopentene-1,2-diyl group, cyclohexene-1,2-diyl group, cycloheptene-1,2-diyl group, and cyclooctene-1,2-diyl group;Examples of divalent gem-hydrocarbon groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,1-diyl group, pentane-1,1-diyl group, hexane-1,1-diyl group, heptane-1,1-diyl group, octane-1,1-diyl group, nonane-1,1-diyl group, decane-1,1-diyl group, cyclopropane-1,1-diyl group, cyclobutane-1,1-diyl group, cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, cycloheptane-1,1-diyl group, cyclooctane-1,1-diyl group, vinylidene group, and propene-1,1-diyl group;

[0073] When such a compound is used as a structural unit of a resin, it provides improved Tg, tensile strength, and elongation, and also provides high solubility in various organic solvents.

[0074] In addition, in this case, X in the general formula (1) 3 is a condensation linking group frequently used in general-purpose polycondensation polymers, especially -CO 2 -, -NR X1 -, -O- are preferable. However, R X1 is the same as above.

[0075] In formula (1), L 1 ~L 2 As the substituent represented by the formula: the following are particularly preferred. However, -* represents a bond. However, the present invention is not limited to these. [ka]

[0076] Furthermore, in the general formula (1), x and y are preferably 0 from the viewpoints of ease of synthesis and availability of raw materials.

[0077] The present invention also provides a resin containing the above-mentioned compound as a structural unit, characterized in that it contains structural units represented by the following general formulas (2) and (3) as a resin that provides particularly excellent physical properties. [ka] (In the formula, Z, 1 ~X 3 , Ar, L 1 ~L 2 , x, y are the same as above. 1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0078] In the formula (3), Y 1represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. Specific examples include ethane-1,1,1,2-tetrayl group, ethane-1,1,2,2-tetrayl group, propane-1,1,1,2-tetrayl group, propane-1,1,2,2-tetrayl group, propane-1,1,1,3-tetrayl group, propane-1,1,2,3-tetrayl group, propane-1,1,3,3-tetrayl group, propane-1,2,2,3-tetrayl group, butane-1,2,3,4-tetrayl group, pentane-1,2,4,5-tetrayl group, hexane-1,2,5,6-tetrayl group, heptane-1,2,6, tetravalent linear saturated hydrocarbon groups such as 2-methylpropane-1,1,1,2-tetrayl group, 2-methylpropane-1,1,2,3-tetrayl group, 2-methylpropane-1,1,3,3-tetrayl group, 2,3-dimethylbutane-1,2,3,4-tetrayl group, 3-methylpentane-1,2,4,5-tetrayl group, 3-methylhexane-1,2,5,6-tetrayl group; cyclopropane-1,1,2,2-tetrayl group, cyclohexane-1,2,5,6-tetrayl group, etc. cyclobutane-1,1,2,2-tetrayl group, cyclobutane-1,1,2,3-tetrayl group, cyclobutane-1,1,2,4-tetrayl group, cyclobutane-1,1,3,3-tetrayl group, cyclobutane-1,2,3,4-tetrayl group, cyclopentane-1,1,2,2-tetrayl group, cyclopentane-1,1,3,3-tetrayl group, cyclopentane-1,1,2,3-tetrayl group, cyclopentane-1,1,2,4-tetrayl group, cyclopentane-1,1,2,5-tetrayl group, cyclopentane-1, tetravalent cyclic saturated hydrocarbon groups such as 1,3,4-tetrayl group, cyclopentane-1,2,3,4-tetrayl group, cyclohexane-1,2,3,4-tetrayl group, cyclohexane-1,2,4,5-tetrayl group, cyclohexane-1,2,3,5-tetrayl group, cycloheptane-1,2,3,4-tetrayl group, cycloheptane-1,2,4,5-tetrayl group, cyclooctane-1,2,3,4-tetrayl group, cyclooctane-1,2,4,5-tetrayl group, and cyclooctane-1,2,5,6-tetrayl group;Tetravalent linear unsaturated hydrocarbon groups such as ethene-1,1,2,2-tetrayl group, propylene-1,1,2,3-tetrayl group, propylene-1,1,3,3-tetrayl group, propylene-1,3,3,3-tetrayl group, propylene-1,2,3,3-tetrayl group, and propylene-2,3,3,3-tetrayl group; cyclopentene-1,2,3,4-tetrayl group, cyclopentene-1,3,4,5-tetrayl group, benzyl Examples of tetravalent unsaturated cyclic hydrocarbon groups include benzene-1,2,3,4-tetrayl group, benzene-1,2,4,5-tetrayl group, naphthalene-1,2,3,4-tetrayl group, naphthalene-1,2,5,6-tetrayl group, naphthalene-1,2,6,7-tetrayl group, naphthalene-1,2,7,8-tetrayl group, naphthalene-2,3,5,6-tetrayl group, and naphthalene-2,3,6,7-tetrayl group.

[0079] Furthermore, the tetravalent hydrocarbon group may have some or all of its hydrogen atoms substituted with the same heteroatoms as above, or may be substituted with a monovalent hydrocarbon group having 1 to 30 carbon atoms optionally containing a heteroatom.

[0080] Furthermore, the tetravalent hydrocarbon group may have some or all of its hydrogen atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and as a result may contain a hydroxyl group, an amino group, a cyano group, a nitro group, a haloalkyl group, etc.

[0081] In addition, the tetravalent hydrocarbon group may have some of its carbon atoms substituted with a substituent containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, may contain an ether bond, a sulfide bond, a carbonyl group, an ester bond, -N(R)- (wherein R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom), an amide bond, an imino bond, a sulfonyl group, a sulfinyl group, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a carbamate bond, a carboxylic acid anhydride (-C(=O)-OC(=O)-), or the like.

[0082] In formula (3), Y 1 As the substituent represented by the formula: the following are particularly preferred. However, -* represents a bond. However, the present invention is not limited to these. [ka]

[0083] Such a resin contains the compound provided by the present invention as a resin constituent unit and contains polyimide units having excellent strength and durability, and thus can achieve high tensile strength, high elongation, and high durability while having excellent solubility in organic solvents.

[0084] The present invention also provides a resin characterized by containing, in addition to the above structural units (2) and (3), a structural unit represented by the following general formula (4): [ka] (In the formula, L 3 is a single bond or a divalent linking group, R 1 ~R 2 Each of w and z independently represents an arbitrary monovalent substituent. When w and z are 2 or more, multiple R 1 and R 2 The substituents represented by may be the same or different.

[0085] In the formula (4), L 3 represents a single bond or a divalent linking group.

[0086] L 3Examples of the divalent linking group that can be used as the linking group include divalent hydrocarbon groups having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom as described above; and divalent heteroatom-containing groups such as an ether bond, a sulfide bond, a carbonyl group, an ester bond, -N(R)- (wherein R is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 29 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom), an amide bond, an imino bond, a sulfonyl group, a sulfinyl group, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a carbamate bond, and a carboxylic anhydride (-C(=O)-OC(=O)-).

[0087] In formula (4), L 3 As the divalent hydrocarbon group that can be used in, the following are particularly suitable, where -* represents a bond, but the present invention is not limited to these. [ka]

[0088] R 1 ~R 2 each independently represents any monovalent substituent.

[0089] R 1 ~R 2 Examples of the monovalent substituent that can be used as the substituent include monovalent hydrocarbon groups having 1 to 30 carbon atoms which may be substituted with the same heteroatoms as described above and which may have a heteroatom interposed therebetween; and monovalent heteroatom-containing groups such as halogen atoms, hydroxyl groups, amino groups, cyano groups, nitro groups, nitroso groups, and mercapto groups.

[0090] Resins containing such units are soluble in basic aqueous solutions and basic organic solvents due to the acidic hydroxyl groups of the phenol units. The water solubility and organic solvent solubility of resins having such properties can be controlled by adding photosensitive or radiation sensitive additives and dissolution control agents, making it possible to perform patterning by lithography.

[0091] L in the general formula (4) 3 As for -CR f1 R f2 -OR-SO 2 - is especially preferable. However, R f1 ~R f2 each independently represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

[0092] R f1 ~R f2 Examples of the fluoroalkyl group that can be used as the fluoroalkyl group include partially fluorinated hydrocarbon groups such as a monofluoromethyl group, a difluoromethyl group, a 2-monofluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group; and perfluoroalkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group.

[0093] Resins containing structural units (4) having such substituents have increased solubility in basic aqueous solutions and basic organic solvents due to the increased acidity of the phenolic hydroxy groups, making them suitable for application to lithography.

[0094] Since the polyimide resin of the present invention is soluble in an aqueous alkaline developer, it can be used for both a positive-type photosensitive resin composition that can be developed with an aqueous alkaline solution and a negative-type photosensitive resin composition that can be developed with an aqueous alkaline solution. Patterns obtained by using these photosensitive resin compositions are fine and have a good pattern shape.

[0095] [Resin manufacturing method] Furthermore, the present invention provides a method for producing the above-mentioned resin, which comprises reacting the above-mentioned compound or an acid halide or an acid anhydride derived therefrom with at least one of the compounds represented by the following general formula (5) and the following general formulas (6) to (7). [ka] (In the formula, Y 1 is the same as above. Y 2 X represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. 4 is a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCO 2 R X4 , -OSO 2 R X4 , -OSO 3 R X4 However, R X4 is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0096] In the formula (7), Y 2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom as described above and which may be interrupted by a heteroatom. X4 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with the same heteroatom as above and which may be interrupted by a heteroatom.

[0097] In formula (7), Y 2 As the substituent represented by the formula: the following are particularly preferred. However, -* represents a bond. However, the present invention is not limited to these. [ka]

[0098] The method for producing a polyimide resin containing structural units represented by the above general formulas (2) and (3) comprises the steps of: 3 Varies depending on the type.

[0099] (Manufacturing method 1) In the general formula (1), X 3 Ga-CO 2 -, -SO 2 -OR-SO 3-, the compound functions as an electrophilic monomer unit in a polycondensation reaction. To express its polymerization activity, the -CO 2 H, -SO 2 H or -SO 3 The H group must be converted to an acid halide or anhydride. Methods for converting the compounds to acid halides include reaction with elemental halogens and with halogen equivalents such as thionyl chloride, oxalyl chloride, sulfuryl chloride, thionyl bromide, oxalyl bromide, sulfuryl bromide, bromine monochloride, and iodine monochloride. Methods for converting the compounds to acid anhydrides include reaction with halogenated carbonates, carbonate anhydrides, acid halides, and carbodiimides.

[0100] The compound represented by the general formula (1) activated by the above method is reacted with any tetracarboxylic dianhydride and any diamine to obtain a polyamic acid having structural units represented by the general formulas (2) and (3) in the main chain.

[0101] Examples of the tetracarboxylic acid dianhydride include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, etc. Examples of aromatic acid dianhydrides include pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,2',3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-terphenyltetracarboxylic acid dianhydride, 3,3',4,4'-oxyphthalic acid dianhydride, 2,3,3',4'-oxyphthalic acid dianhydride, 2,3,2',3'-oxyphthalic acid dianhydride, diphenylsulfone-3,3',4,4'-tetracarbazone, and the like. carboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-(3,4-dicarboxyphenoxy) Benzene dianhydride, p-phenylene bis(trimellitic acid monoester acid anhydride), bis(1,3-dioxo-1,3-dihydroisobenzfuran-5-carboxylic acid) 1,4-phenylene, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)fluorene dianhydride 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,Examples of the dianhydride include, but are not limited to, 2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and acid dianhydride compounds in which the aromatic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0102] Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3,4,5- Tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6,3,0,0 2,6]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,1]heptane tetracarboxylic dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanhydride Examples of the dianhydride include, but are not limited to, tetrathane-1,2,8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and "Rikacid" (registered trademark) BT-100 (all trade names, manufactured by New Japan Chemical Co., Ltd.) and their derivatives, as well as acid dianhydride compounds in which the alicyclic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0103] Examples of the aliphatic acid dianhydride include, but are not limited to, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof.

[0104] These aromatic acid dianhydrides, alicyclic acid dianhydrides, and aliphatic acid dianhydrides can be used alone or in combination of two or more kinds.

[0105] Examples of the diamine include hydroxyl group-containing diamine, aromatic diamine, alicyclic diamine, aliphatic diamine, etc. Preferred hydroxyl group-containing diamines include, but are not limited to, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)propane, etc.

[0106] Examples of aromatic diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'3,3'-tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2'3,3'-tetrachlorobenzidine, m-phenylene Examples of the diamine compound include, but are not limited to, phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminobenzanilide, and diamine compounds in which the aromatic ring of these compounds is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0107] Examples of alicyclic diamines include cyclobutanediamine, isophoronediamine, bicyclo[2,2,1]heptanebismethylamine, tricyclo[3,3,1,13,7]decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4, 4'-Diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-aminocyclohexyl)propane, Examples of the diamine compound include, but are not limited to, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl)propane, and diamine compounds in which the alicyclic ring of these compounds is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0108] Examples of aliphatic diamines include alkylene diamines such as ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane; ethylene glycol diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, and bis(3-aminopropyl)ether; and siloxane diamines such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, and α,ω-bis(3-aminopropyl)polydimethylsiloxane, but are not limited thereto.

[0109] These hydroxyl group-containing diamines, aromatic diamines, alicyclic diamines, and aliphatic diamines may be used alone or in combination of two or more kinds.

[0110] Siloxane diamines can also be suitably used.

[0111] Furthermore, in addition to the above monomer units, a diamine compound capable of forming the unit represented by the general formula (4) in the polymer can be used.

[0112] (Manufacturing method 2) In the general formula (1), X 3 -CONR X1 -, -O-, -NR X1 -, -S-, -SO 2 NR X1 In the case where the formula (1) is -, the compound functions as a nucleophilic monomer unit in a polycondensation reaction. In this case, the compound is reacted with any tetracarboxylic dianhydride and any diamine to obtain a polyamic acid having structural units represented by the above general formulas (2) and (3) in the main chain.

[0113] In the above method, the same tetracarboxylic dianhydrides and diamines as described above can be used.

[0114] Furthermore, in addition to the above monomer units, any carboxylic acid represented by the above general formula (7) or an acid halide or acid anhydride derived therefrom can be used.

[0115] Examples of the carboxylic acid represented by the general formula (7) or an acid halide or an acid anhydride derived therefrom include, for example, 3,4'-diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl methane-3,4'-dicarboxylic acid, diphenyl methane-4,4'-dicarboxylic acid, diphenyl sulfone-3,3'-dicarboxylic acid, diphenyl sulfone-3,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, diphenyl Diphenylsulfide-3,4'-dicarboxylic acid, diphenylsulfide-4,4'-dicarboxylic acid, 1,4-bis(4-carboxyphenoxy)benzene, phthalic acid, terephthalic acid, isophthalic acid, biphenyldicarboxylic acid, 2,2'-bis(trifluoromethyl)biphenyldicarboxylic acid, 3,3'-bis(trifluoromethyl)biphenyldicarboxylic acid, 2,2'-dimethylbiphenyldicarboxylic acid, 3,3'-dimethylbiphenyldicarboxylic acid, 2,2',3,3'-tetramethylbiphenyldicarboxylic acid dicarboxylic acid, 2,2'-dichlorobiphenyldicarboxylic acid, 3,3'-dichlorobiphenyldicarboxylic acid, 2,2'3,3'-tetrachlorobiphenyldicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, bis(4-carboxyphenoxyphenyl)sulfone, bis(3-carboxyphenoxyphenyl)sulfone, bis[4-(3-carboxyphenoxy)phenyl]sulfone, bis(4-carboxyphenoxy)biphenyl, bis{4-(4-carboxyphenoxy)phenyl}ether, 1,4-bis(4-carboxyphenoxy)benzene, 9,9-bis(4-carboxyphenyl)fluorene, 2,2'-bis[3-(3-carboxybenzamido)-4-carboxyphenyl]hexafluoropropane, 4-carboxyphenyl-4'-carboxybenzoate, 4,4'-dicarboxybenzanilide, or dicarboxylic acids in which the aromatic rings of these are substituted with alkyl groups, alkoxy groups, halogen atoms, or the like;Cyclobutanedicarboxylic acid, isophoronedicarboxylic acid, bicyclo[2,2,1]heptanediacetic acid, tricyclo[3,3,1,13,7]decane-1,3-dicarboxylic acid, 1,2-cyclohexyldicarboxylic acid, 1,3-cyclohexyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 4,4'-cyclohexylmethanedicarboxylic acid, 3,3'-dimethyl-4,4'-cyclo 4,4'-Dicyclohexylmethanedicarboxylic acid, 3,3'-diethyl-4,4'-cyclohexylmethanedicarboxylic acid, 3,3',5,5'-tetramethyl-4,4'-dicyclohexylmethanedicarboxylic acid, 3,3',5,5'-tetraethyl-4,4'-dicyclohexylmethanedicarboxylic acid, 3,5-diethyl-3',5'-dimethyl-4,4'-dicyclohexylmethanedicarboxylic acid, 4,4'-dicyclohexyl ether dicarboxylic acid, 3,3'-dimethyl-4,4'-dicyclohexyl ether dicarboxylic acid, 3,3'-diethyl-4,4'-dicyclohexyl ether dicarboxylic acid, 3,3',5,5'-tetramethyl-4,4'-dicyclohexyl ether dicarboxylic acid, 3,3',5,5'-tetraethyl-4,4'-dicyclohexyl ether dicarboxylic acid, 3,5-diethyl-3',5'-dimethyl-4,4'-dicyclohexyl ether dicarboxylic acid, 2,2-bis(4-carboxycyclohexyl)propane, 2,2-bis(3-methyl-4-carboxycyclohexyl)propane 2,2-bis(3-ethyl-4-carboxycyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-carboxycyclohexyl)propane, 2,2-bis(3,5-diethyl-4-carboxycyclohexyl)propane, 2,2-(3,5-diethyl-3',5'-dimethyl-4,4'-dicarboxydicyclohexyl)propane, or diol compounds in which the alicyclic ring of these is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like;Examples of the dicarboxylic acids include alkylene dicarboxylic acids such as ethanedicarboxylic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, 1,5-pentanedicarboxylic acid, 1,6-hexanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid; polyether dicarboxylic acids such as bis(carboxymethyl)ether, bis(2-carboxyethyl)ether, and siloxane dicarboxylic acids such as 1,3-bis(3-carboxypropyl)tetramethyldisiloxane, 1,3-bis(4-carboxybutyl)tetramethyldisiloxane, and α,ω-bis(3-carboxypropyl)polydimethylsiloxane, as well as acid halides and acid anhydrides derived therefrom, but are not limited thereto. These dicarboxylic acids and acid halides or acid anhydrides derived therefrom can be used alone or in combination of two or more kinds.

[0116] In the synthesis of polyamic acid, the proportions of the compound represented by the above general formula (1), diamine, tetracarboxylic dianhydride, and other dicarboxylic acid derivatives are appropriately determined depending on the molecular weight of the polyimide, etc., and in the general formula (1), X 3 Ga-CO 2 -, -SO 2 -OR-SO 3 In the case where X is -, the molar ratio of the compound represented by the above general formula (1), the tetracarboxylic dianhydride and the dicarboxylic acid derivative to the diamine is usually in the range of 0.90 to 1.10, preferably 0.95 to 1.05, and more preferably 0.98 to 1.02. 3 -CONR X1 -, -O-, -NR X1 -, -S-, -SO 2 NR X1 In this case, the molar ratio of the compound represented by the above general formula (1) and diamine to the tetracarboxylic dianhydride and dicarboxylic acid derivative is usually in the range of 0.90 to 1.10, preferably 0.95 to 1.05, and more preferably 0.98 to 1.02.

[0117] The reaction of the compound represented by the above general formula (1), diamine, tetracarboxylic dianhydride, and other dicarboxylic acid derivatives is usually carried out by mixing the respective monomer components in a solvent at 0 to 80°C, preferably 10 to 50°C.

[0118] Specific examples of the solvent include ethers such as tetrahydrofuran and anisole, ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone, esters such as butyl acetate, methyl benzoate, and γ-butyrolactone, cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and aromatic hydrocarbons such as toluene and xylene. Preferred are ketones, esters, and amides, and particularly preferred are γ-butyrolactone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. Usually, the concentration of the polyimide is adjusted to be 10 to 40% by mass in consideration of the dissolution viscosity and the like.

[0119] Next, a non-polar solvent such as xylene that is azeotropic with water is added to the reaction liquid of the polyamic acid obtained above, and the mixture is heated to 100 to 200°C, preferably 130 to 180°C, to carry out a dehydration ring-closing reaction while removing water generated from the reaction system, thereby obtaining a polyimide resin containing structural units represented by the general formulas (2) and (3) above.

[0120] (Molecular weight of polymer and introduction of end-capping agent) The suitable weight average molecular weight of the polyimide resin containing the structural unit (2) and the structural unit (3), or the polyimide resin containing the structural unit (2), the structural unit (3) and the structural unit (4) is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, it becomes easy to form a film of a desired thickness on a substrate from a photosensitive resin composition using the polyimide resin as a base resin, and if the molecular weight is 100,000 or less, the viscosity of the photosensitive resin composition does not become extremely high, and there is no risk of it being impossible to form a film. In the present invention, the weight average molecular weight is a value measured in terms of polystyrene by gel permeation chromatography (GPC).

[0121] The polyimide resin containing the structural unit (2) and the structural unit (3), or the polyimide resin containing the structural unit (2), the structural unit (3) and the structural unit (4), may be capped at both ends with a terminal capping agent for the purpose of controlling the molecular weight in the condensation polymerization reaction and suppressing the change in the molecular weight of the obtained polymer over time, i.e., gelation. Examples of terminal capping agents that react with acid dianhydrides include monoamines and monohydric alcohols. Examples of terminal capping agents that react with diamine compounds include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, vinyl ethers, and the like. In addition, various organic groups can be introduced as terminal groups by reacting with a terminal capping agent.

[0122] Examples of monoamines used as a blocking agent for the acid anhydride group terminal include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, Aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, nylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl 6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0123] On the other hand, examples of monohydric alcohols that can be used as a blocking agent for the acid anhydride group terminals include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2 ... Canol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-icosanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl 1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7 dimethyl-3-octanol, 2,4 dimethyl-1-heptanol, 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norborneol, and terpineol, but are not limited thereto. These may be used alone or in combination of two or more.

[0124] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds that can be used as the amino end capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene Phthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid Monocarboxylic acids such as 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which the carboxyl group of these acids is converted into an acid chloride, as well as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,Examples of the monoacid chloride compounds include monoacid chloride compounds in which only the monocarboxyl groups of dicarboxylic acids such as 3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene are acid chloride compounds, and active ester compounds obtained by reacting the monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

[0125] Examples of the dicarbonate compound used as a blocking agent for the amino group terminal include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0126] Examples of vinyl ether compounds used as a blocking agent for the amino group terminal include butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether, and benzyl vinyl ether.

[0127] Other compounds used as a capping agent for amino group terminals include chloroformates such as benzyl chloroformate, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, allyl chloroformate, tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, and isopropyl chloroformate; isocyanate compounds such as butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, and phenyl isocyanate; benzoyl chloride, methanesulfonyl chloride, and p-toluenesulfonyl chloride.

[0128] The introduction ratio of the blocking agent for the acid anhydride group terminal is preferably in the range of 0.1 to 60 mol %, particularly preferably 5 to 50 mol %, and further preferably 5 to 20 mol %, based on the tetracarboxylic dianhydride components represented by the above general formulas (1) and (5), which are the raw materials for the polyimide resin of the present invention. The introduction ratio of the blocking agent for the amino group terminal is preferably in the range of 0.1 to 100 mol %, particularly preferably 5 to 90 mol %, based on the diamine component. A plurality of different terminal blocking agents may be reacted to introduce a plurality of different terminal groups.

[0129] The polyimide resin of the present invention may contain a polyimide structural unit other than the structural unit represented by the above-mentioned general formula (2) or the structural unit represented by the general formula (3), a structural unit of a polyimide precursor, a polybenzoxazole structural unit, or a structural unit of a polybenzoxazole precursor.

[0130] [Photosensitive resin composition] Next, a photosensitive resin composition using the polyimide resin of the present invention as a base resin will be described. In the present invention, a positive-type photosensitive resin composition or a negative-type photosensitive resin composition can be obtained by using the above-mentioned polyimide resin of the present invention as a base resin.

[0131] [Positive-type photosensitive resin composition] First, in the photosensitive resin composition based on the polyimide resin of the present invention, an alkali-developable positive photosensitive resin composition will be described. The positive photosensitive resin composition of the present invention can be, for example, in the two forms described below, but is not limited thereto.

[0132] In the present invention (A) a resin containing structural units represented by the above general formulas (2) and (3); (B) a photosensitizer that generates an acid when exposed to light and increases its dissolution rate in an alkaline aqueous solution, the photosensitizer having a quinone diazide structure, and (D) a solvent, The present invention provides a positive-type photosensitive resin composition comprising:

[0133] In addition, the positive photosensitive resin composition may further contain (C) one or more crosslinking agents selected from an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'). [ka] (In the formula, the dotted line represents a bond, and R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.

[0134] In this way, by using the photosensitizer of component (B), the exposed area becomes soluble in an alkaline aqueous developer at a high dissolution rate during pattern formation, while the unexposed area does not dissolve because the photosensitizer prevents dissolution in alkaline solutions, and a positive image can be obtained. The resins containing the structural units represented by the above general formulae (2) and (4) are themselves alkaline soluble, so that pattern deterioration such as residues such as scum and footing is less likely to occur at the bottom of the open pattern, and are advantageous in fine pattern formation.

[0135] (First form) A first embodiment of the positive photosensitive resin composition of the present invention is (A) a polyimide resin containing structural units represented by the above general formulas (2) and (3); (B) a photosensitizer that generates an acid when exposed to light and increases its dissolution rate in an alkaline aqueous solution, the photosensitizer having a quinone diazide structure, and (D) a solvent, It includes.

[0136] In terms of obtaining alkali solubility of the positive photosensitive resin composition of the present invention, when the resin containing the structural units (2) and (3) has a structural unit represented by the general formula (4), it can be described by the number of moles of phenolic hydroxyl groups in 100 g of component (A). That is, in 100 g of component (A), the number of moles of phenolic hydroxyl groups is 0.10 mol or more and 0.40 mol or less, more preferably 0.20 mol or more and 0.35 mol or less, and most preferably 0.25 mol or more and 0.35 mol or less. If the number of moles of phenolic hydroxyl groups is 0.10 mol or more, a desired alkali dissolution rate can be obtained in a developer which is an aqueous alkaline solution, and during pattern formation, there is no problem in opening the pattern, and no scum is observed at the bottom of the pattern, and there is no risk of loss of resolution. On the other hand, the amount of phenolic hydroxyl groups that can be introduced into 100 g of component (A) can be about 0.40 mol in the design of the polyimide resin of the present invention. In this case, the highest solubility in the alkaline aqueous developer can be expected. However, after patterning using the photosensitive resin composition of the present invention, post-curing can be performed to form a cured film, but there is a risk that a large amount of alkali-soluble phenolic hydroxyl groups remain in this cured film, and there is a concern that the resistance of the obtained cured film to alkaline chemicals will be impaired, so a preferred amount of phenolic hydroxyl groups to be introduced is a small amount that can provide alkali solubility.

[0137] The component (B) in the positive photosensitive resin composition of the present invention is a photosensitizer that generates an acid by exposure to light and increases the dissolution rate in an alkaline aqueous solution, and is a compound having a quinone diazide structure. An example of the component (B) is a compound having a 1,2-naphthoquinone diazide sulfonyl group in the molecule.

[0138] Examples of compounds having a 1,2-naphthoquinone diazide sulfonyl group in the molecule include compounds having a 1,2-naphthoquinone diazide sulfonyl group in the molecule, which are represented by the following general formula (8) or (9), where -* represents a bond.

[0139] [ka]

[0140] Specifically, trihydroxybenzophenone or tetrahydroxybenzophenone, a ballast molecule having a phenolic hydroxyl group and represented by the following general formula (10), or a novolak resin having a repeating unit represented by the below-mentioned formula (15) and a weight average molecular weight in the range of 2,000 to 20,000, preferably 3,000 to 10,000, is preferably used as the compound into which the 1,2-naphthoquinone diazide sulfonyl group is introduced. That is, the following resins or compounds having a phenolic hydroxyl group in which the hydrogen atom of the phenolic hydroxyl group is substituted with the above 1,2-naphthoquinone diazide sulfonyl group are preferably used as the component (B). [ka]

[0141] Here, R 101 ~R 106 are each independently a hydrogen atom, a methyl group, a group represented by the following formula (11) or a group represented by the following formula (12). w is an integer of 0 to 2, z is an integer of 0 to 2, and when z is 0, w is 1 or 2. When z is 0 and w is 1, A is a hydrogen atom, a methyl group, or a group represented by the following formula (11). When z is 0 and w is 2, one of A is a methylene group or a group represented by the following formula (13) and the other is a hydrogen atom, a methyl group, or a group represented by the following formula (11). When z is 1, A is a methylene group or a group represented by the following formula (13). When z is 2 and w is 1, A is a methine group or a group represented by the following formula (14), and when w is 2, one of A is a methylene group or a group represented by the following formula (13) and the other is a methine group or a group represented by the following formula (14). [ka] (In the formula, a1, a2, a3, a4, a5, a6, and a7 are each an integer of 0 to 3, and a1+a2≦5, a3+a4≦4, and a6+a7≦3.)

[0142] In this case, it is preferable that the low-molecular-weight compound (ballast molecule) of the above formula (10) has 2 to 20 benzene rings, more preferably 2 to 10 benzene rings, and further preferably 3 to 6 benzene rings, and that the ratio of the number of phenolic hydroxyl groups to the number of benzene rings is 0.5 to 2.5, more preferably 0.7 to 2.0, and further preferably 0.8 to 1.5.

[0143] Specific examples of such low molecular weight molecules (ballast molecules) include the following (B-1) to (B-44).

[0144] [ka]

[0145] [ka]

[0146] Among the low-molecular-weight compounds (ballast molecules) exemplified above, (B-3), (B-29), (B-33), (B-38), etc. are preferably used, and compounds in which the hydrogen atoms of the phenolic hydroxyl groups of these ballast molecules are substituted with 1,2-naphthoquinone diazide sulfonyl groups are preferably used as the component (B) of the positive-type photosensitive resin composition of the present invention.

[0147] [ka] (In the formula, mm is an integer of 0 to 3.)

[0148] The novolak resin having the repeating unit represented by the above formula (15) can be synthesized by condensing a phenol represented by the following formula (16), specifically at least one phenol such as o-cresol, m-cresol, p-cresol, 3,5-xylenol, etc., with an aldehyde by a conventional method.

[0149] [ka] (In the formula, mm is an integer of 0 to 3.)

[0150] In this case, examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde, with formaldehyde being preferred.

[0151] The molar ratio of the phenol represented by the above formula (16) to the aldehyde is preferably 0.2 to 2, particularly preferably 0.3 to 2.

[0152] As a method for introducing 1,2-naphthoquinone diazide sulfonyl groups into the compound to which the 1,2-naphthoquinone diazide sulfonyl groups are to be introduced, it is preferable to use a dehydrochlorination condensation reaction between 1,2-naphthoquinone diazide sulfonyl chloride and a phenolic hydroxyl group using a base catalyst. In the case of the ballast molecule represented by the above formula (10), trihydroxybenzophenone or tetrahydroxybenzophenone, the ratio of the hydrogen atoms of the phenolic hydroxyl groups substituted with the 1,2-naphthoquinone diazide sulfonyl groups is 10 to 100 mol%, preferably 50 to 100 mol%, and in the case of the novolak resin having a repeating unit represented by the above formula (15), the ratio of the hydrogen atoms of the phenolic hydroxyl groups substituted with the 1,2-naphthoquinone diazide sulfonyl groups is 2 to 50 mol%, preferably 3 to 27 mol%.

[0153] The amount of the component (B) added is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the component (A). One or more types of the component (B) can be used in combination.

[0154] By incorporating such a component (B), the dissolution inhibition of the component (B) suppresses the solubility in an alkaline aqueous solution before exposure, making the system alkali-insoluble, and upon exposure, the photosensitizer of the component (B) generates an acid by light, increasing the dissolution rate in an alkaline aqueous solution and making the system alkali-soluble. In other words, when an alkaline aqueous solution is used as the developer, the unexposed areas do not dissolve in the developer, and the exposed areas are soluble in the developer, making it possible to form a positive pattern.

[0155] Next, the component (D) in the positive photosensitive resin composition of the first embodiment is a solvent. The solvent for the component (D) is not limited as long as it dissolves the components (A) and (B). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone. One or more of these may be used. Particularly, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or a mixed solvent thereof is preferred.

[0156] The amount of component (D) blended is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, per 100 parts by mass of the total amount of components (A) and (B).

[0157] (Second Form) Next, the positive photosensitive resin composition according to the second embodiment of the present invention will be described. A second embodiment of the positive photosensitive resin composition of the present invention is a positive photosensitive resin composition comprising the above-mentioned (A), (B), and (D), and further comprising (C) one or more crosslinking agents selected from an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'). [ka] (In the formula, the dotted line represents a bond, and R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.

[0158] As the components (A) and (B) of the positive photosensitive resin composition of the second embodiment of the present invention, the same components as those of the first positive photosensitive resin composition described above can be suitably used.

[0159] The component (C) in the positive photosensitive resin composition of the second embodiment of the present invention is one or more crosslinking agents selected from an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups (alkoxymethyl groups) per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'). [ka] (In the formula, the dotted line represents a bond, and R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.

[0160] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0161] The above-mentioned melamine condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by first modifying a melamine monomer with formalin by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol to obtain a modified melamine represented by the following general formula (17).The above-mentioned alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0162] [ka] (In the formula, R 12 may be the same or different and are a methylol group, an alkoxymethyl group containing an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, provided that at least one of them is a methylol group or the above alkoxymethyl group.

[0163] Above R 12 Examples of the alkyl group include a methylol group, an alkoxymethyl group such as a methoxymethyl group or an ethoxymethyl group, and a hydrogen atom.

[0164] Specific examples of modified melamine represented by the above general formula (17) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Next, the modified melamine represented by the above general formula (17) or its multimer (e.g., oligomer such as dimer or trimer) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is reached, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0165] The preparation of the urea condensate modified with formaldehyde or formaldehyde-alcohol may be carried out, for example, by modifying a urea condensate having a desired molecular weight with formaldehyde by methylolation, or by further modifying the urea condensate by alkoxylation with an alcohol, according to a known method. Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate.

[0166] The modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0167] Next, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulas (C-3) to (C-7). [ka]

[0168] The above crosslinking agents can be used alone or in combination of two or more.

[0169] On the other hand, examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups or groups having a glycidyl group include compounds obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Suitable examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups or groups having a glycidyl group include the compounds represented by the following formulas (C-8) to (C-14).

[0170] [ka] (In the formula, t is 2≦t≦3. (t is not limited to an integer.))

[0171] One or two of these polyhydric phenol compounds in which the hydroxyl groups are substituted with, for example, glycidoxy groups can be used as the crosslinking agent.

[0172] Examples of compounds in which the hydrogen atoms of the hydroxyl groups of a polyhydric phenol are substituted with the substituents represented by the following formula (C-1) include compounds containing two or more of the above substituents and represented by the following formula (C-15). [ka] (In the formula, the dotted lines represent bonds.) [ka] (In the formula, 1≦u≦3.)

[0173] On the other hand, examples of the compound containing two or more groups represented by the following formula (C-2) (nitrogen atoms having glycidyl groups) include those represented by the following formula (C-16). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.) [ka] (In the formula, W represents a linear, branched or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group.)

[0174] Examples of the compound represented by the above formula (C-16) include compounds represented by the following formulae (C-17) to (C-20). [ka]

[0175] On the other hand, as a compound containing two or more groups represented by the above formula (C-2') (nitrogen atoms having glycidyl groups), a compound represented by the following formula (C-21) can be preferably used. [ka]

[0176] One or two of these compounds containing two or more groups represented by the above formula (C-2) or (C-2') can be used as the crosslinking agent.

[0177] The component (C) is a component that undergoes a crosslinking reaction during post-curing after pattern formation of the positive photosensitive resin composition using the polymer containing the polyimide precursor of the present invention, thereby further increasing the strength of the cured product. From the viewpoints of photocurability and heat resistance, the weight-average molecular weight of such component (C) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0178] The amount of the component (C) blended in the positive photosensitive resin composition of the second embodiment of the present invention is preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, per 100 parts by mass of the component (A).

[0179] As the solvent for the component (D) in the positive photosensitive resin composition of the second embodiment of the present invention, the same solvents as those explained in the positive photosensitive resin composition of the first embodiment can be preferably mentioned.

[0180] (Other Ingredients) The positive photosensitive resin composition of the present invention may further contain components other than the components (A), (B), (C) and (D). Examples of the other components include an adhesion aid and a surfactant (E). As the surfactant (E), the following compounds can be suitably used.

[0181] The (E) surfactant is preferably a nonionic surfactant, such as a fluorine-based surfactant, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane compound, etc.

[0182] As these surfactants, commercially available ones can be used, for example, Fluorad "FC-4430" (manufactured by Sumitomo 3M Limited), Surflon "S-141" and "S-145" (both manufactured by Asahi Glass Co., Ltd.), Unidyne "DS-401", "DS-4031" and "DS-451" (both manufactured by Daikin Industries, Ltd.), Megafac "F-8151" (manufactured by DIC Corporation), "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Among these, Fluorad "FC-4430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable.

[0183] [Negative-type photosensitive resin composition] Next, an alkali-developable negative photosensitive resin composition will be described in the photosensitive resin composition based on the polyimide resin of the present invention. The negative photosensitive resin composition of the present invention can be, for example, in the form described below, but is not limited thereto.

[0184] In the present invention (A') a resin containing structural units represented by the above general formulas (2) and (3); (B') a photoacid generator, (C') one or more crosslinking agents selected from an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'), [ka] (In the formula, the dotted line represents a bond, and R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2. (D) a solvent, The present invention provides a negative type photosensitive resin composition comprising:

[0185] In this way, by using the photoacid generator, component (B'), in pattern formation, an acid can be generated in the exposed areas, and the crosslinking groups of the added crosslinking agent, component (C'), can be crosslinked with the crosslinking reaction points of the polymer, making the exposed areas insoluble in a developer, thereby providing a composition that gives a negative image.

[0186] The negative type photosensitive resin composition of the present invention has the following form: (A') a polyimide resin containing structural units (2) and (3); (B') a photoacid generator, (C') one or more crosslinking agents selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'), [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.) (D) a solvent, The negative type photosensitive resin composition comprises:

[0187] The component (A') of the negative photosensitive resin composition in the present invention is a polyimide resin containing the structural unit (5), and the same resins as those in the above-mentioned positive photosensitive resin composition can be suitably used.

[0188] The negative type photosensitive resin composition of the present invention can be produced by crosslinking the crosslinking groups of component (C') with the polymer of component (A') using the acid generated from component (B') as a catalyst.

[0189] The component (B') of the negative photosensitive resin composition in the present invention is a photoacid generator. As the photoacid generator, a material that generates an acid by irradiation with light having a wavelength of 190 to 500 nm and that serves as a curing catalyst can be used. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives, imide-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0190] The onium salt includes, for example, a compound represented by the following general formula (18). [ka] (In the formula, R 13 represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, which may have a substituent; M + represents an iodonium cation or a sulfonium cation; K - represents a non-nucleophilic counterion, and j is 2 or 3.

[0191] Above R 13 In the above formula, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aryl group include a phenyl group; an alkoxyphenyl group such as an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, or an m- or p-tert-butoxyphenyl group; and an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like.

[0192] K - Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonates such as triflate, 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate and 1,2,3,4,5-pentafluorobenzenesulfonate; and alkylsulfonates such as mesylate and butanesulfonate.

[0193] The diazomethane derivative includes a compound represented by the following general formula (19). [ka] (In the formula, R 14 may be the same or different and represent a linear, branched, or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0194] Above R 14 In the above, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. Examples of the aryl group include a phenyl group; an alkoxyphenyl group such as an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, and a m- or p-tert-butoxyphenyl group; and an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and a 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0195] Specific examples of such photoacid generators include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, )phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate and other onium salts;Bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane diazomethane derivatives such as 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane;Bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis -o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime glyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc. oxime derivatives; oxime sulfonate derivatives such as α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile; β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane; disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone; nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;Sulfonic acid ester derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene; phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene 2,3-dicarboximido-yl-triflate, 5-norbornene 2,3-dicarboximido-yl-tosylate, 5-norbornene 2,3-dicarboximido-yl-n-butylsulfonate, n-trifluoromethanesulfonyloxy ... Examples of the imido-yl-sulfonate derivatives include ethylsulfonyloxynaphthylimide; iminosulfonates such as (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, and 2-methyl-2[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane. Among these, imido-yl-sulfonates, iminosulfonates, oxime sulfonates, and the like are preferably used. The above photoacid generators may be used alone or in combination of two or more kinds.;

[0196] From the viewpoints of the light absorption of the photoacid generator itself and the photocurability in a thick film, the amount of the photoacid generator (B') in the negative type photosensitive resin composition of the present invention is preferably 0.05 to 20 parts by mass, and particularly preferably 0.2 to 5 parts by mass, per 100 parts by mass of the component (A').

[0197] As the component (C') of the negative photosensitive resin composition of the present invention, the same crosslinking agent as the component (C) explained in the second embodiment of the positive photosensitive resin composition can be preferably used.

[0198] As described above, the (C') component of the negative photosensitive resin composition of the present invention is a component that can form a negative pattern by crosslinking the crosslinking group of the (C') component with the polymer of the (A') component using the acid generated from the (B') component as a catalyst, and also causes a crosslinking reaction during post-curing after pattern formation, thereby further increasing the strength of the cured product. From the viewpoints of photocurability and heat resistance, the weight-average molecular weight of such a (C') component is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0199] The amount of the component (C') blended in the negative photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, per 100 parts by mass of the component (A).

[0200] The component (D) in the negative photosensitive resin composition of the present invention is a solvent. The solvent for the component (D) is not limited as long as it dissolves the components (A'), (B'), and (C'). Examples of the component (D) include the same solvents as those exemplified in the first or second embodiment of the positive photosensitive resin composition.

[0201] The negative photosensitive resin composition of the present invention may further contain other components in addition to the components (A'), (B'), (C'), and (D). Examples of other components include a sensitizer (F), an adhesion aid, a polymerization inhibitor for enhancing storage stability, and a surfactant (E) commonly used for improving coatability. The surfactant (E) may be preferably the same as that described in the positive photosensitive resin composition.

[0202] Examples of the sensitizer (F) include 7-N,N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3'-carbonylbis(7-N,N-diethylamino)coumarin, 3,3'-carbonylbis(7-N,N-dimethoxy)coumarin, 3-thienylcarbonyl-7-N,N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N,N-methoxycoumarin, 3-(4'-methoxybenzoyl)coumarin, 3,3'-carbonylbis-5,7-(dimethoxy)coumarin, benzalacetophenone, 4'-N,N-dimethylaminobenzalacetophenone, 4'-acetaminobenzal-4-methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, and 4,4'-bis(N-ethyl,N-methyl)benzophenone. The content of these is preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyimide precursor polymer of the present invention.

[0203] In addition, in the negative photosensitive resin composition of the present invention, a basic compound can be added as component (G) as necessary. As the basic compound, a compound capable of suppressing the diffusion speed of the acid generated by the photoacid generator when it diffuses through the resist film is suitable. And, by adding the basic compound, the resolution can be improved, the sensitivity change after exposure can be suppressed, the substrate dependency and the environment dependency can be reduced, and the exposure margin and the pattern shape can be improved.

[0204] Examples of the basic compound include ammonia, primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and further compounds represented by the following general formula (20). [ka]

[0205] In the formula, p=1, 2, or 3. The side chains α may be the same or different and may be any of the substituents represented by the following general formulae (21) to (23). The side chains β may be the same or different and represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether bond or a hydroxyl group. The side chains α may be bonded to each other to form a ring. [ka]

[0206] Here, R 300 , R 302 , R 305 is a linear or branched alkylene group having 1 to 4 carbon atoms, R 301 , R 304 R is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain one or more hydroxyl groups, ether bonds, ester bonds or lactone rings. 303 is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R 306 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may contain one or more hydroxyl groups, ether bonds, ester bonds or lactone rings. Note that *- indicates a bond end.

[0207] Examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.

[0208] Examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine.

[0209] Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, and the like.

[0210] Examples of mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

[0211] Examples of aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives Examples of the conductors include quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.

[0212] Examples of nitrogen-containing compounds having a carboxyl group include aminobenzoic acid, indole carboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), and the like.

[0213] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridine sulfonic acid and pyridinium p-toluenesulfonate.

[0214] Examples of nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2 ... Examples include 1-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyyurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, and N-(2-hydroxyethyl)isonicotinamide.

[0215] Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, etc. Examples of the imide derivatives include phthalimide, succinimide, maleimide, etc.

[0216] Examples of the compound represented by the above general formula (20) include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, tris[2-(2-methoxyethoxymethoxy)ethyl]amine, tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine, tris[2-(1-ethoxypropoxy)ethyl]amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxaoxa -1,10-diazabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isopropyl ... butyryloxyethyl)amine, tris(2-valeryloxyethyl)amine, tris(2-pivaloyloxyethyl)amine, N,N-bis(2-acetoxyethyl) 2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl]amine, tris[2-(tert-butoxycarbonylmethyloxy)ethyl ]amine, tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl) 2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl) 2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl) 2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl) 2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(2-oxopropoxycarbonyl)ethylamine amine, N,N-bis(2-hydroxyethyl)2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)2-(4-formyloxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)2-(2-formyloxyethoxycarbonyl)ethylamine, N,N-bis(2-methoxyethyl)2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxy Examples of the basic compounds include, but are not limited to, one or more of the above basic compounds.

[0217] From the viewpoint of sensitivity, the amount of the basic compound added in the negative photosensitive resin composition of the present invention is preferably 0 to 3 parts by mass, and particularly preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (A).

[0218] [Pattern formation method] Furthermore, in the present invention, (1) applying the positive photosensitive resin composition onto a substrate to form a photosensitive film; (2) heating the photosensitive film; (3) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (4) developing with an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of:

[0219] In this way, the positive photosensitive resin composition of the present invention can be subjected to alkaline development using an aqueous alkaline solution.

[0220] Furthermore, in the present invention, (I) applying the negative photosensitive resin composition onto a substrate to form a photosensitive film; (II) a step of heating the photosensitive film; (III) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (IV) developing with an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of:

[0221] When the base resin of the negative photosensitive resin composition of the present invention contains the structural unit represented by the above general formula (4), good alkaline development with an aqueous alkaline solution becomes possible.

[0222] In this case, it is preferable to include a post-exposure baking step between the step (III) and the step (IV).

[0223] In particular, in the case of a negative-type photosensitive resin composition containing a polymer containing a resin that contains structural units represented by the above general formulas (2) and (4), by including a step of heating after exposure (post-exposure bake (PEB)), the crosslinking reaction between the crosslinking group of the crosslinking agent and the crosslinking reaction point of the polymer can be promoted using the acid generated from the photoacid generator by exposure as a catalyst.

[0224] Next, a pattern forming method using the positive-type photosensitive resin composition and the negative-type photosensitive resin composition of the present invention will be described.

[0225] In either case of the positive-type photosensitive resin composition of the present invention or the negative-type photosensitive resin composition, a pattern can be formed by adopting a known lithography technique. For example, a silicon wafer or a SiO 2 A photosensitive resin composition is applied by spin coating onto a substrate, a SiN substrate, or a substrate on which a pattern of copper wiring or the like has been formed, and pre-baked at 80 to 130°C for about 50 to 600 seconds to form a photosensitive film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

[0226] In the spin coating method, the photosensitive resin composition is applied onto a silicon substrate by dispensing about 5 mL of the photosensitive resin composition onto the substrate and then rotating the substrate. At this time, the thickness of the photosensitive film on the substrate can be easily adjusted by adjusting the rotation speed. The remaining solvent can then be removed by pre-baking.

[0227] Next, a mask for forming a desired pattern is placed over the photosensitive film, and high-energy rays such as i-rays and g-rays with wavelengths of 190 to 500 nm or electron beams are irradiated at an exposure dose of 1 to 5,000 mJ / cm. 2 Approximately, preferably 100 to 2,000 mJ / cm 2 Irradiate to a degree.

[0228] Next, if necessary, post-exposure baking (PEB) may be performed on a hot plate at 60 to 150° C. for 1 to 10 minutes, preferably at 80 to 120° C. for 1 to 5 minutes.

[0229] In the positive photosensitive resin composition and the negative photosensitive resin composition of the first and second embodiments of the present invention, any of the compositions can be subjected to alkaline development using an aqueous alkaline solution.

[0230] On the other hand, a suitable alkaline aqueous solution that can be used for alkaline development is a 2.38% aqueous solution of tetramethylhydroxyammonium (TMAH). Development can be carried out by a normal method such as a spray method or a paddle method, or by immersion in a developer. Thereafter, washing, rinsing, drying, etc. can be carried out as necessary to obtain a resist film having a desired pattern.

[0231] Furthermore, the present invention provides a method for forming a cured coating, which includes a step of post-curing the patterned coating obtained by the above-mentioned pattern formation method by heating at a temperature of 100 to 300°C.

[0232] That is, the patterned coating obtained by the above-mentioned pattern forming method can be heated and post-cured using an oven or a hot plate at a temperature of 100 to 300°C, preferably 150 to 300°C, and more preferably 180 to 250°C, to form a cured coating. If the post-curing temperature is 100 to 300°C, the crosslink density of the coating of the photosensitive resin composition can be increased and residual volatile components can be removed, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, and further electrical properties. The post-curing time can be 10 minutes to 10 hours.

[0233] The present invention also provides an interlayer insulating film comprising a cured film obtained by curing the above-mentioned positive-type photosensitive resin composition or the above-mentioned negative-type photosensitive resin composition.

[0234] The above-mentioned formed patterns are used for the purpose of forming protective coatings (interlayer insulating films) that cover wiring, circuits, substrates, etc., and these formed patterns and protective coatings have excellent insulating properties and also exhibit excellent adhesion to the wiring they cover, metal layers such as Cu in the circuit, metal electrodes present on the substrate, or insulating substrates such as SiN present on the wiring or circuit they cover, and can significantly improve the resolution performance to enable the formation of even finer patterns while retaining the mechanical strength suitable for a protective coating.

[0235] The present invention also provides a surface protective film comprising a cured coating formed by curing the above-mentioned positive-type photosensitive resin composition or the above-mentioned negative-type photosensitive resin composition.

[0236] The cured coating obtained as described above has excellent adhesion to substrates, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions and the like. It also has excellent reliability for semiconductor elements using it as a protective coating, and is particularly capable of preventing cracks from occurring during temperature cycle tests. It is therefore suitable for use as a surface protective coating for electrical and electronic components, semiconductor elements and the like.

[0237] The above protective coatings (interlayer insulating films, surface protective films) are effective for applications such as insulating films for semiconductor elements including rewiring applications, insulating films for multilayer printed circuit boards, solder masks, and coverlay films due to their heat resistance, chemical resistance, and insulating properties.

[0238] That is, the present invention also provides an electronic component having the above-mentioned interlayer insulating film or surface protective film.

[0239] The resin of the present invention contains structural units represented by the above general formulas (2) and (3), and therefore has excellent electrical properties, mechanical properties, and adhesion, is soluble in an alkaline developer, and can form fine patterns with high resolution. These cured coatings having patterns can be used as excellent protective coatings for electrical and electronic components and insulating protective coatings. Electronic components having these cured coatings can also be provided.

[0240] In the future, as chips become denser and more highly integrated, the rewiring technology for insulating protective films will likely require increasingly finer patterns. The photosensitive resin composition using the polyimide resin of the present invention can realize high resolution and meet the demand for finer patterns without impairing the excellent mechanical properties, particularly strength, and adhesion, of the polyimide patterns and protective films obtained by heating.

[0241] It is also strongly desired that the insulating protective film that has been patterned and cured be endowed with heat resistance in the various processes and resistance to the various chemicals used, and the cured coating (interlayer insulating film, surface protective film) of the present invention can meet this demand.

[0242] Thus, the compound and polyimide resin of the present invention can provide an excellent photosensitive resin composition that possesses all of these characteristics without lacking any one of them. EXAMPLES

[0243] The present invention will be specifically described below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples.

[0244] The chemical structural formulas of the compounds used in the following synthesis examples are shown below. [ka]

[0245] [Synthesis Example 1] Dicarboxylic acid (X CA Synthesis of -1) To a mixture of 25 g (143 mmol) of methyl 4-(cyanomethyl)benzoate, 77 g (357 mmol) of 1,4-dibromobutane, and 0.8 g (3.6 mmol) of benzyltriethylammonium chloride, 114 g (1.43 mol) of 50% aqueous sodium hydroxide was added dropwise at 70°C and the mixture was allowed to react for 6 hours. The reaction solution was cooled to room temperature, the liquid in the flask was removed, and the remaining gummy precipitate was washed several times with toluene. While cooling with ice, 200 mL of 50% aqueous sulfuric acid was added, and the mixture was allowed to react for one week under reflux conditions. The precipitated solid was filtered, washed with isopropyl ether, and dried under reduced pressure to obtain dicarboxylic acid (X CA -1) was obtained in an amount of 17 g.

[0246] [Synthesis Example 2] Dicarboxylic acid (X CA Synthesis of -2) In Synthesis Example 1, 1,4-dibromobutane was replaced with 82 g of 1,5-dibromopentane, and the rest was treated in the same manner as in Synthesis Example 1 to obtain dicarboxylic acid (X CA -2) was obtained in an amount of 10 g.

[0247] [Synthesis Example 3] Dicarboxylic acid (X CA Synthesis of -3) In Synthesis Example 1, methyl 4-(cyanomethyl)benzoate was replaced with 25 g of methyl 2-(cyanomethyl)benzoate, and the rest was mixed in the same manner to prepare dicarboxylic acid (X CA -3) was obtained in an amount of 18 g.

[0248] [Synthesis Example 4] Dicarboxylic acid (X CA Synthesis of -4) In Synthesis Example 2, methyl 4-(cyanomethyl)benzoate was replaced with 25 g of methyl 2-(cyanomethyl)benzoate, and the same procedure was repeated to prepare dicarboxylic acid (X CA -4) was obtained in an amount of 12 g.

[0249] [ka]

[0250] [Synthesis Example 5] Diamine (X AM Synthesis of -1) Dicarboxylic acid (X CA12.7g of thionyl chloride was added dropwise to a mixture of 5g of IM-1), 78mg of N,N-dimethylformamide, and 50g of chloroform, and the mixture was allowed to react under reflux conditions for 24 hours. After the solvent was distilled off under reduced pressure, 15g of methylene chloride was added to the dicarboxylic acid chloride obtained, and 43g of 2M ammonia-methanol solution was added dropwise, followed by stirring at room temperature for 24 hours. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography to obtain 3.7g of diamide compound (IM-1). 5.5g of 1,8-diazabicyclo[5.4.0]undec-7-ene was added dropwise to a mixture of diamide compound (IM-1), 4.5g of 1,3-dibromo-5,5-dimethylhydantoin, and 400mL of methanol, followed by stirring for 15 minutes under reflux conditions, and then 4.5g of 1,3-dibromo-5,5-dimethylhydantoin was added and stirred for 1 hour. After the solvent was distilled off under reduced pressure, 200 g of ethyl acetate and 100 g of water were added and stirred. After the aqueous layer was removed, the organic layer was washed with water, a saturated aqueous solution of sodium bicarbonate, and saturated saline. After the solvent was distilled off under reduced pressure, the obtained crude product was purified by column chromatography to obtain diamine (X AM -1) 2.2g was obtained.

[0251] [Synthesis Example 6] Diamine (X AM Synthesis of -2) In Synthesis Example 5, dicarboxylic acid (X CA -1) was mixed with the dicarboxylic acid (X CA -3) 5g, and the rest was the same as above. AM -2) 2.4g was obtained.

[0252] [ka]

[0253] [Synthesis Example 7] Dicarboxylic acid (X CA -5) Synthesis The dicarboxylic acid (X CATo the dicarboxylic acid chloride prepared from 5 g of (-1), 6.5 g of 4-hydroxybenzoic acid and 50 g of methylene chloride were added and stirred. The reaction solution was cooled on ice, and a mixed solution of 11 g of triethylamine, 260 mg of N,N-dimethylaminopyridine, and 10 g of methylene chloride was added dropwise, and the reaction was carried out at room temperature for 24 hours. The reaction was stopped with 50 g of 5% hydrochloric acid, and the precipitated solid was collected by filtration, washed with tert-butyl methyl ether, and then dried to obtain dicarboxylic acid (X CA -5) 6g was obtained.

[0254] [Synthesis Example 8] Diamine (X AM Synthesis of -3) The dicarboxylic acid (X CA To the dicarboxylic acid chloride prepared from 5 g of (-1), 6.5 g of 4-nitrophenol and 50 g of methylene chloride were added and stirred. The reaction solution was ice-cooled, and a mixed solution of 11 g of triethylamine, 260 mg of N,N-dimethylaminopyridine, and 10 g of methylene chloride was added dropwise, and the mixture was reacted at room temperature for 24 hours. Next, 100 g of diisopropyl ether was added, and the mixture was stirred for 1 hour under ice cooling, and the precipitated solid was collected by filtration. The obtained solid was stirred at 60°C for 24 hours together with 30 g of saturated aqueous ammonium chloride solution and 7 g of zinc. The reaction solution was ice-cooled, and 50 g of 20% hydrochloric acid was added dropwise, and the mixture was stirred for 8 hours to dissolve the zinc. The precipitated solid was collected by filtration, suspended in a saturated aqueous sodium bicarbonate solution, and stirred for 1 hour, and then the solid was collected by filtration and washed several times with ice-cooled acetonitrile. The solid was dried under reduced pressure to obtain diamine (X AM -3) 4.9g was obtained.

[0255] [Synthesis Example 9] Synthesis of polyamide-imide resin (A-1) In a 300 ml flask equipped with a stirrer and a thermometer, 10 g (27.3 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.32 g (2.94 mmol) of p-aminophenol, and 40 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. CA-1) 1.38g (5.87mmol) was dissolved in 50g of N-methyl-2-pyrrolidone, to which 698mg (5.87mmol) of thionyl chloride was added dropwise under ice cooling, and the solution was heated to room temperature and stirred for 3 hours to prepare a dicarboxylic acid chloride solution, to which 7.29g (23.5mmol) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA) was added and dissolved, and then added dropwise to the previously prepared N-methyl-2-pyrrolidone solution of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. After stirring at room temperature for 3 hours, 15g of xylene was added to the reaction solution, and the mixture was heated to reflux at 180℃ for 6 hours while removing the water generated from the system. After cooling to room temperature, the reaction solution was added dropwise to 650 mL of ultrapure water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain polyamideimide resin (A-1). The molecular weight of this polymer was measured by GPC and found to be 32,000 in terms of polystyrene.

[0256] [Synthesis Example 10] Synthesis of polyamide-imide resin (A-2) In Synthesis Example 9, dicarboxylic acid (X CA 2) with the dicarboxylic acid (X CA A polyamideimide resin (A-2) was obtained by the same procedure, except that 1.46 g (5.87 mmol) of 1-2) was used instead. The molecular weight of this polymer was measured by GPC and found to be 33,000 in terms of polystyrene.

[0257] [Synthesis Example 11] Synthesis of polyamide-imide resin (A-3) In Synthesis Example 9, dicarboxylic acid (X CA 3) was added to the dicarboxylic acid (X CA A polyamideimide resin (A-3) was obtained by the same procedure, except that 1.38 g (5.87 mmol) of 1-3) was used instead. The molecular weight of this polymer was measured by GPC and found to be 30,000 in terms of polystyrene.

[0258] [Synthesis Example 12] Synthesis of polyamide-imide resin (A-4) In Synthesis Example 9, dicarboxylic acid (XCA -1) obtained in Synthesis Example 4 was used instead of the dicarboxylic acid (X CA -4) 1.46 g (5.87 mmol), and a polyamideimide resin (A-4) was obtained in the same formulation otherwise. When the molecular weight of this polymer was measured by GPC, the weight average molecular weight was 31,000 in terms of polystyrene.

[0259] [Synthesis Example 13] Synthesis of polyimide resin (A-5) Into a 300 ml flask equipped with a stirrer and a thermometer, 10 g (27.3 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the diamine (X AM -1) 1.32 g (7.48 mmol), p-aminophenol 0.41 g (3.74 mmol), and 40 g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. To this solution, a solution prepared by dissolving 11.6 g (37.4 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA) in 50 g of N-methyl-2-pyrrolidone was added dropwise. After stirring at room temperature for 3 hours, 15 g of xylene was added to this reaction solution, and heating reflux was carried out for 6 hours while removing the water generated at 180 °C outside the system. After cooling to room temperature, this reaction solution was added dropwise with stirring to 650 mL of ultrapure water, the precipitate was filtered off, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain a polyimide resin (A-5). When the molecular weight of this polymer was measured by GPC, the weight average molecular weight was 30,000 in terms of polystyrene.

[0260] [Synthesis Example 14] Synthesis of polyimide resin (A-6) In Synthesis Example 13, the diamine (X AM -1) was replaced with the diamine (X AM -2) 1.46 g (5.87 mmol) obtained in Synthesis Example 6, and a polyimide resin (A-6) was obtained in the same formulation otherwise. When the molecular weight of this polymer was measured by GPC, the weight average molecular weight was 30,000 in terms of polystyrene.

[0261] [Synthesis Example 15] Synthesis of polyamideimide resin (A-7) In Synthesis Example 9, the dicarboxylic acid (X CAThe dicarboxylic acid (X CA A polyamideimide resin (A-7) was obtained by the same procedure, except that 2.79 g (5.87 mmol) of 2-5) was used instead. The molecular weight of this polymer was measured by GPC and found to be 32,000 in terms of polystyrene.

[0262] [Synthesis Example 16] Synthesis of polyimide resin (A-8) In Synthesis Example 13, diamine (X AM The diamine (X AM A polyimide resin (A-8) was obtained by the same procedure, except that 3.12 g (7.48 mmol) of 3-3) was used instead. The molecular weight of this polymer was measured by GPC and found to be 31,000 in terms of polystyrene.

[0263] [Comparative Synthesis Example 1] Synthesis of polyimide resin (A-9) In a 300 ml flask equipped with a stirrer and a thermometer, 10 g (27.3 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.32 g (2.94 mmol) of p-aminophenol, and 40 g of N-methyl-2-pyrrolidone were added and dissolved at room temperature. 9.11 g (29.4 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA) was added to 50 g of N-methyl-2-pyrrolidone and dissolved, and then added dropwise to the previously prepared N-methyl-2-pyrrolidone solution of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. After stirring at room temperature for 3 hours, 15 g of xylene was added to the reaction solution, and the mixture was heated to reflux at 180°C for 6 hours while removing the water generated from the system. After cooling to room temperature, the reaction solution was added dropwise to 650 mL of ultrapure water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain polyimide resin (A-9). The molecular weight of this polymer was measured by GPC and found to be 35,000 in terms of polystyrene.

[0264] [Comparative Synthesis Example 2] Synthesis of polyamide-imide resin (A-10) In Synthesis Example 9, dicarboxylic acid (XCA A polyamideimide resin (A-10) was obtained by the same procedure except that 1.43 g (5.87 mmol) of 4,4'-biphenyldicarboxylic acid was used instead of 1.43 g of 4,4'-biphenyldicarboxylic acid. The molecular weight of this polymer was measured by GPC and found to be 29,000 in terms of polystyrene.

[0265] [Comparative Synthesis Example 3] Synthesis of polyamide-imide resin (A-11) In Synthesis Example 9, dicarboxylic acid (X CA A polyamideimide resin (A-11) was obtained by the same procedure except that 1.19 g (5.87 mmol) of sebacic acid was used instead of 1.19 g of sebacic acid. The molecular weight of this polymer was measured by GPC and found to be 34,000 in terms of polystyrene.

[0266] [Comparative Synthesis Example 4] Synthesis of polyimide resin (A-12) In Synthesis Example 13, diamine (X AM A polyimide resin (A-12) was obtained by the same procedure except that 1.38 g (7.48 mmol) of 4,4'-benzidine was used instead of -1). The molecular weight of this polymer was measured by GPC and found to be 31,000 in terms of polystyrene.

[0267] [Comparative Synthesis Example 5] Synthesis of polyimide resin (A-13) In Synthesis Example 13, diamine (X AM A polyimide resin (A-13) was obtained by the same procedure except that 2.19 g (7.48 mmol) of 1,4-bis(4-aminophenoxy)benzene was used instead of -1). The molecular weight of this polymer was measured by GPC and found to be 32,000 in terms of polystyrene.

[0268] [Comparative Synthesis Example 6] Synthesis of polyimide resin (A-14) In Synthesis Example 13, diamine (X AMA polyimide resin (A-14) was obtained by the same procedure except that 2.61 g (7.48 mmol) of 9,9'-bis(4-aminophenyl)fluorene was used instead of 1)-1. The molecular weight of this polymer was measured by GPC and found to be 32,000 in terms of polystyrene.

[0269] [Comparative Synthesis Example 7] Synthesis of polyimide resin (A-15) In Synthesis Example 13, diamine (X AM A polyimide resin (A-15) was obtained by the same procedure except that 1.99 g (7.48 mmol) of 4,4'-cyclohexylidene dianiline was used instead of -1). The molecular weight of this polymer was measured by GPC and found to be 32,000 in terms of polystyrene.

[0270] II. Preparation of Photosensitive Resin Composition Resins (A-1) to (A-8) synthesized in Synthesis Examples 9 to 16 and resins (A-9) to (A-15) synthesized in Comparative Synthesis Examples 1 to 7 were used as base resins to prepare resin compositions of 30 mass% resin equivalent with the composition and blending amounts shown in Table 1. After stirring, mixing, and dissolving, the mixture was microfiltered with a 1.0 μm Teflon (registered trademark) filter to obtain a photosensitive resin composition. In the table, the solvent PGMEA stands for propylene glycol monomethyl ether acetate, and GBL stands for gamma-butyrolactone.

[0271] [Table 1]

[0272] Photosensitive resin compositions 1 to 8 shown in Table 1 relate to the above-mentioned positive photosensitive resin compositions of the present invention. Comparative photosensitive resin compositions 1 to 7 are the above-mentioned positive photosensitive resin compositions of the present invention, in which the polymers synthesized in Comparative Synthesis Examples 1 to 7 were used as the base resin instead of the polymer of the present invention. [Table 2]

[0273] Photosensitive resin compositions 9 to 16 shown in Table 2 relate to the above-mentioned negative type photosensitive resin composition of the present invention. Comparative photosensitive resin compositions 8 to 14 are the above-mentioned negative type photosensitive resin compositions of the present invention, in which the polymers synthesized in Comparative Synthesis Examples 1 to 7 were used as the base resin instead of the polymer of the present invention.

[0274] In Tables 1 and 2, the details of the quinone diazide compound photosensitizer (photosensitizer 1), photoacid generator (photoacid generator 1), and crosslinkers (CL-1) to (CL-3) are as follows:

[0275] Photosensitizer (Photosensitizer 1) [ka] (In the formula, Q represents a 1,2-naphthoquinone diazide sulfonyl group represented by the following formula (24) or a hydrogen atom, and 90% of Q is substituted with a 1,2-naphthoquinone diazide sulfonyl group represented by the following formula (24).) [ka]

[0276] Photoacid generator (Photoacid generator 1) [ka]

[0277] Crosslinker (CL-1) [ka]

[0278] Crosslinker (CL-2) Epoxy resin: ADEKA Corporation EP4000L

[0279] Crosslinker (CL-3) [ka]

[0280] III. Pattern Formation The above-mentioned photosensitive resin compositions 1 to 16 and comparative photosensitive resin compositions 1 to 14 were dispensed on a silicon substrate in an amount of 5 mL, and then the substrate was rotated, i.e., by a spin coating method, so that the film thickness would be 10 μm after heating for post-curing performed after pattern formation. That is, after considering in advance that the film thickness would decrease after the post-curing process, the rotation speed during application was adjusted so that the finished film thickness after post-curing would be 10 μm. Next, the substrate was prebaked on a hot plate at 100°C for 2 minutes. Next, an i-line stepper NSR-2205i11 manufactured by Nikon Corporation was used to perform i-line exposure and pattern formation. In forming the pattern, a mask for a positive pattern or a negative pattern was used as appropriate according to the photosensitive resin composition used. The mask had a pattern capable of forming 20 μm holes in a 1:1 vertical and horizontal arrangement, and was capable of forming hole patterns at 10 μm intervals from 50 μm to 20 μm, 5 μm intervals from 20 μm to 10 μm, and 1 μm intervals from 10 μm to 1 μm.

[0281] Next, a heating step (post-exposure bake) was carried out under the conditions shown in Table 4 below.

[0282] In the development process, an alkaline aqueous solution was used as the developer, and a 2.38% aqueous solution of tetramethylammonium hydroxide was used as the developer. After puddle development with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute was performed three times, rinsing with ultrapure water was performed.

[0283] The resulting pattern on the substrate was then post-cured in an oven at 200° C. for 2 hours while purging with nitrogen.

[0284] Next, each substrate was cut out so that the shape of the obtained hole pattern could be observed, and the hole pattern shape was observed using a scanning electron microscope (SEM). The diameter of the smallest opening hole at a film thickness of 10 μm after post-curing was determined, and the shape of the pattern was evaluated. Together with these results, the sensitivity at which the smallest pattern could be formed is shown in Tables 3 and 4.

[0285] The hole pattern shape was evaluated according to the following criteria, and the evaluation results are shown in Tables 3 and 4. The composition was not a homogeneous solution and was deemed unevaluable if it was cloudy. Good: Holes that are rectangular or tapered (the dimensions at the top of the hole are larger than the dimensions at the bottom) Defective: Reverse taper shape (the dimensions of the top of the hole are smaller than the dimensions of the bottom), overhang shape (the top of the hole protrudes), significant film loss is observed, or residue is observed at the bottom of the hole.

[0286] IV. Breaking elongation, breaking strength The above-mentioned photosensitive resin compositions 1 to 16 and comparative photosensitive resin compositions 1 to 14 were spin-coated on an aluminum substrate so that the final film thickness after curing was 10 μm. Then, the coating was pre-baked on a hot plate at 110° C. for 4 minutes to obtain a photosensitive resin film.

[0287] Then, the curing was carried out in an oven at 200°C for 2 hours while purging with nitrogen, to obtain a photosensitive resin cured film. Next, the wafer with the cured film was cut into strips with a width of 10 mm and a length of 60 mm, and the cured film was peeled off from the substrate by immersing it in 20% by mass hydrochloric acid. The breaking elongation and breaking strength of the obtained cured film were measured using an autograph AGX-1KN manufactured by Shimadzu Corporation. The measurement was carried out 10 times for each sample, and the average values ​​are shown in Table 2. The breaking elongation is preferably large, more preferably 20% or more. The breaking strength is preferably large, more preferably 100 MPa or more.

[0288] V. Solvent solubility Resins (A-1) to (A-15) synthesized in the above Synthesis Examples 9 to 16 and Comparative Synthesis Examples 1 to 7 were used as base resins to prepare 30% by mass propylene glycol monomethyl ether acetate resin solutions. After stirring overnight, the state of the solution was evaluated as follows in Table 3: transparent (◯), cloudy (△), and insoluble or gelled (×).

[0289] First, the results of patterning using the positive photosensitive resin compositions (photosensitive resin compositions 1 to 8, comparative photosensitive resin compositions 1 to 7) and the results of the breaking elongation, breaking strength, and solvent solubility of the cured films are shown in Table 3. The solvent solubility in the table is for the resins (A-1) to (A-15) contained in the photosensitive resin compositions 1 to 8 and the comparative photosensitive resin compositions 1 to 7, respectively.

[0290] [Table 3]

[0291] As shown in Table 3, the positive photosensitive resin composition of the present invention exhibited a good pattern shape in alkaline aqueous solution development, and the minimum hole dimension was smaller than the finished film thickness of 10 μm, indicating that an aspect ratio of 1 or more could be achieved.

[0292] Furthermore, as shown in Table 3, it was found that a cured film having good solvent solubility and good mechanical properties was obtained, that is, the cured film had both good mechanical properties and good solvent solubility.

[0293] On the other hand, the cured film using the comparative photosensitive resin composition 2, 4-6 has mechanical properties equivalent to those of the cured film obtained from the composition of the present invention, but the solvent solubility of the resin is low (Comparative Examples 2, 4-6), and the cured film having excellent solvent solubility has poor mechanical properties (Comparative Examples 1, 3, 7). Thus, it was found that it is difficult to achieve both of the above-mentioned performances with the cured film using the comparative photosensitive resin composition that uses a resin that does not contain the structural unit represented by the general formula (2) as the base resin. In particular, the cured film of Comparative Example 6, which used a resin incorporating a 9,9-diphenylfluorene skeleton (see Patent Document 5), had mechanical properties comparable to those of the Examples, but the resin had low solvent solubility, and the cured film of Comparative Example 7, which used a resin having a 1,1-diphenylcyclohexane structure (see Patent Document 6), had a certain degree of solvent solubility, but the strength of the cured film was not as good as that of the Examples. Therefore, it is clear that simply containing a cardo structure as a structural unit does not allow the cured film to have both mechanical properties and solvent solubility, as in the present invention.

[0294] Next, the results of patterning using the negative photosensitive resin compositions (photosensitive resin compositions 9 to 16, comparative photosensitive resin compositions 8 to 14) and the breaking elongation and breaking strength of the cured films are shown in Table 4. The solvent solubilities of the resins (A-1) to (A-15) contained in the photosensitive resin compositions 9 to 16 and comparative photosensitive resin compositions 8 to 14, respectively, are as shown in Table 3.

[0295] [Table 4]

[0296] As shown in Table 4, the negative type photosensitive resin composition of the present invention exhibited a good pattern shape in alkaline aqueous solution development, and the minimum hole dimension was smaller than the finished film thickness of 10 μm, indicating that an aspect ratio of 1 or more could be achieved.

[0297] Furthermore, as shown in Table 4, it was found that a cured film having good solvent solubility and good mechanical properties was obtained, that is, the cured film had both good mechanical properties and good solvent solubility.

[0298] On the other hand, the cured films obtained using the comparative photosensitive resin compositions had mechanical properties (elongation at break, strength at break) equivalent to those of the cured films obtained from the compositions of the present invention, and none of them had excellent solvent solubility. Thus, it was found that it is difficult to achieve both of the above-mentioned properties with the cured films obtained using the comparative photosensitive resin compositions that use as their base resin a resin that does not contain a structural unit represented by general formula (2).

[0299] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A resin comprising structural units represented by the following general formulas (2) and (3): [Formula 1] (In the formula, Z represents a linear, branched or cyclic divalent hydrocarbon group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. X １ ~X ３ Ha-CO ２ --, --CONR Ｘ１ -, -O-, -NR Ｘ１ -, -S-, -SO ２ -, -SO ３ -, -SO ２ N.R. Ｘ１ -, which may be the same or different. Ｘ１ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. Ar is a divalent aromatic group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L １ ~L ２ each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. x and y each independently represent 0 or 1. Y １ represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

2. In the general formula (2), X ３ Ga-CO ２ --, --NR Ｘ１ 2. The resin according to claim 1, wherein the substituent is any one of --, --O--.

3. 3. The resin according to claim 1, wherein x and y in the general formula (2) are 0.

4. The resin according to any one of claims 1 to 3, characterized in that, in addition to the structural units (2) and (3), it further contains a structural unit represented by the following general formula (4): [chemical 2] (In the formula, L ３ is a single bond or a divalent linking group, R １ ~R ２ Each of w and z is independently an arbitrary monovalent substituent. When w and z are 2 or more, a plurality of R １ and R ２ The substituents represented by may be the same or different.

5. L in the general formula (4) ３ -CR ｆ１ R ｆ２ -or-SO ２ -, where R ｆ１ ~R ｆ２ and each independently represent a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

6. A method for producing a resin, comprising reacting (i) a compound represented by the following general formula (1) or an acid halide or an acid anhydride derived therefrom with (ii) a compound represented by the following general formula (5) and (iii) at least one compound represented by the following general formulas (6) to (7): [C3] (In the formula, Z represents a linear, branched or cyclic divalent hydrocarbon group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. X １ ~X ３ Ha-CO ２ --CONR Ｘ１ -, -O-, -NR Ｘ１ -, -S-, -SO ２ -, -SO ３ -, -SO ２ N.R. Ｘ１ -, which may be the same or different. Ｘ１ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. Ar is a divalent aromatic group having 2 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L １ ~L ２each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom; and each of x and y independently represents 0 or 1. [C4] (In the formula, Y １ represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. ２ represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. ４ is a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCO ２ R Ｘ４ , -OSO ２ R Ｘ４ , -OSO ３ R Ｘ４ Here, R Ｘ４ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

7. (A) a resin according to any one of claims 1 to 5; (B) a photosensitizer that generates an acid when exposed to light and increases its dissolution rate in an alkaline aqueous solution, the photosensitizer having a quinone diazide structure, and (D) a solvent, A positive-type photosensitive resin composition comprising:

8. The positive photosensitive resin composition according to claim 7, further comprising one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'). [C5] (In the formula, the dotted line represents a bond, and R ｃ represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2.

9. (A') the resin according to any one of claims 1 to 5; (B') a photoacid generator, (C') one or more crosslinking agents selected from an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing two or more groups represented by the following formula (C-2) or (C-2'), [C6] (In the formula, the dotted line represents a bond, and R ｃ represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s is 1 or 2. (D) a solvent, A negative type photosensitive resin composition comprising:

10. (1) A step of applying the positive photosensitive resin composition according to claim 7 or 8 onto a substrate to form a photosensitive film; (2) a step of heating the photosensitive film; (3) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (4) developing with an aqueous alkaline developer; A pattern forming method comprising the steps of:

11. (I) a step of applying the negative photosensitive resin composition according to claim 9 onto a substrate to form a photosensitive film; (II) a step of heating the photosensitive film; (III) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (IV) developing with an aqueous alkaline developer; A pattern forming method comprising the steps of:

12. 12. The method for forming a pattern according to claim 11, further comprising a post-exposure baking step between the step (III) and the step (IV).

13. A method for forming a cured coating, comprising a step of post-curing the patterned coating obtained by the method for forming a pattern according to any one of claims 10 to 12 by heating at a temperature of 100 to 300°C.

14. 10. An interlayer insulating film comprising a cured film obtained by curing the positive-type photosensitive resin composition according to claim 7 or 8, or the negative-type photosensitive resin composition according to claim 9.

15. 10. A surface protective film comprising a cured coating formed by curing the positive-type photosensitive resin composition according to claim 7 or 8, or the negative-type photosensitive resin composition according to claim 9.

16. 16. An electronic component comprising the interlayer insulating film according to claim 14 or the surface protective film according to claim 15.

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