Photosensitive resin composition, photosensitive resin sheet, cured product, method for producing cured product, semiconductor device, display device, and method for producing resin

Abstract

The purpose of the present invention is to provide a high-sensitivity photosensitive resin composition with which the amount of film reduction during alkaline development is small and the exposure time can be shortened. The present invention is a photosensitive resin composition comprising: (A) one or more resins selected from the group consisting of polyimides containing specific constituent units, polybenzoxazoles, polyamides, and copolymers of the polyimides, the polybenzoxazoles, the polyamides, and the copolymers of the polyimides, the polybenzoxazoles, the polyamides; (B) a photoacid generator; and (C) a solvent containing (C1) a specific ketone compound and / or (C2) a specific ketone compound.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin sheet, a cured product, a method for producing a cured product, a semiconductor device, a display device, and a method for producing a resin. Background Art

[0002] For surface protection films or interlayer insulating films used in semiconductor devices, insulating layers of organic electric field light-emitting elements, or planarizing films of thin film transistor (TFT) substrates, polyimides or polybenzoxazoles with excellent heat resistance, electrical insulation, and mechanical properties are widely used. In recent years, photosensitive resin compositions that impart photosensitivity to these resins themselves or their precursors (hereinafter, these photosensitive resin compositions are referred to as polyimide-based photosensitive resin compositions) have been used. By using polyimide-based photosensitive resin compositions, the pattern processing process can be simplified and the complicated manufacturing process can be shortened.

[0003] Regarding polyimide-based photosensitive resin compositions, positive materials in which the exposed portion is easily soluble in a developer and pattern processing is possible, and negative materials in which the composition itself is easily soluble and the exposed portion is insoluble in a developer are proposed. As polyimide-based photosensitive resin compositions, those obtained by adding a quinonediazide compound to polyimide, polybenzoxazole, a polyimide precursor or a polybenzoxazole precursor (for example, see Patent Document 1), or those obtained by adding a photoacid generator to a polyamide containing a protective group that can be detached in the presence of an acid (for example, see Patent Document 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2011-180473

[0007] Patent Document 2: Japanese Patent Application Publication No. 2011-221173 Summary of the invention

[0008] Problems to be solved by the invention

[0009] In recent years, due to the increase in the size of substrates used and the improvement in productivity, in order to shorten the exposure time and further improve the aperture ratio and in-plane uniformity of film thickness after development, it has become a problem to reduce the amount of film reduction in the unexposed part during development.

[0010] The technology described in Patent Document 1 is a technology that combines an alkali-soluble resin with a quinonediazide. The quinonediazide compound interacts with the alkali-soluble resin to reduce the solubility of the composition relative to the alkaline developer. On the other hand, since it becomes an indene carboxylic acid compound due to the photochemical reaction caused by exposure, it acts as a dissolution promoter relative to the alkaline developer, so that a dissolution contrast is shown between the unexposed part and the exposed part, so that pattern processing can be performed. Therefore, the sensitivity depends on the amount of quinonediazide compound added. However, if the amount of quinonediazide compound added is increased, the photochemical reaction rate is reduced due to the light absorption of the quinonediazide compound itself. Therefore, it is difficult to take into account both the shortening of the exposure time and the small amount of film reduction.

[0011] The technology of Patent Document 2 is a technology that replaces the hydrogen atoms of the hydroxyl groups in the alkali-soluble polyamide with a tert-butoxycarbonyl group (hereinafter, also referred to as a t-Boc group) to make an alkali-insoluble resin, and combines it with a photoacid generator. The technology can generate an acid from the photoacid generator in the exposed part, and the acid reacts with the t-Boc group to make the t-Boc group detach from the polyamide (hereinafter, referred to as deprotection), thereby changing the polyamide from alkali-insoluble to alkali-soluble. Therefore, it is a technology that generates a dissolution contrast between the exposed part and the unexposed part, and pattern processing can be performed. In the technology, there is a problem that the reaction rate of the t-Boc group with the acid is low and the exposure time cannot be shortened.

[0012] Technical means of solving problems

[0013] The present invention is as follows.

[0014] (1) A photosensitive resin composition comprising: (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, comprising a constituent unit represented by formula (1);

[0015] (B) a photoacid generator; and

[0016] (C) a solvent,

[0017] The (C) solvent includes (C1) a ketone compound represented by the formula (2) and / or (C2) a ketone compound represented by the formula (3).

[0018] [Chemistry 1]

[0019]

[0020] (In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2is a monovalent oxymethyl group having 3 to 20 carbon atoms; m represents an integer of 0 to 4, n represents an integer of 1 to 4; * represents a bonding site, and a and b each independently represent an integer of 1 or 2)

[0021] [Chemistry 2]

[0022]

[0023] (In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4 represents a monovalent organic group having 1 to 5 carbon atoms; p represents an integer of 1 or 2; in formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2))

[0024] (2) The photosensitive resin composition according to (1), wherein the resin (A) contains a polyimide including a structural unit represented by formula (1).

[0025] (3) The photosensitive resin composition according to (1) or (2), wherein the component (C1) and / or the component (C2) contains a ketone compound having a boiling point of 100° C. or higher and 170° C. or lower under standard pressure.

[0026] (4) The photosensitive resin composition according to any one of (1) to (3), comprising the component (C2), wherein the component (C2) comprises a ketone compound wherein q=2 and r=0 in the formula (3).

[0027] (5) The photosensitive resin composition according to any one of (1) to (4), wherein the content of the compound represented by formula (4) is 0.3% by mass or less when the total amount of the photosensitive resin composition is 100% by mass.

[0028] [Chemistry 3]

[0029]

[0030] (In formula (4), R 6 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, R 7 Each independently represents a monovalent organic group having 1 to 12 carbon atoms, s represents an integer of 2 to 3, and t represents an integer satisfying 0≦t≦(s+1))

[0031] (6) The photosensitive resin composition according to any one of (1) to (5), further comprising a compound represented by formula (5) and / or a compound represented by formula (6),

[0032] When the total amount of the photosensitive resin composition is 100 mass %, the total content of the compound represented by formula (5) and the compound represented by formula (6) is 0.0001 mass % or more and 0.03 mass % or less.

[0033] [Chemistry 4]

[0034]

[0035] (In formula (5), R 8 represents a monovalent organic group having 1 to 6 carbon atoms, R 9 and R 10 Each independently represents a monovalent organic group having 1 to 3 carbon atoms; in formula (6), R 11 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and u represents an integer greater than 0)

[0036] (7) The photosensitive resin composition according to any one of (1) to (6), further comprising an organic acid having a pKa of -2 to 1.

[0037] (8) The photosensitive resin composition according to any one of (1) to (7), wherein the content of fluorine atoms contained in all the resins is greater than 15% by mass when the total amount of all the resins contained in the photosensitive resin composition is 100% by mass.

[0038] (9) A photosensitive resin sheet obtained by forming the photosensitive resin composition according to any one of (1) to (8) into a sheet on a support.

[0039] (10) A cured product obtained by curing the photosensitive resin composition according to any one of (1) to (8).

[0040] (11) A method for producing a cured product, comprising: a) applying the photosensitive resin composition according to any one of (1) to (8) onto a substrate and drying the coating to form a photosensitive resin film, or using the photosensitive resin sheet according to (9) to thermally press-bond the photosensitive resin composition of the present invention onto a substrate;

[0041] b) exposing the photosensitive resin film or the photosensitive resin composition after thermal compression bonding;

[0042] c) a step of washing or removing the exposed portion of the photosensitive resin film or the exposed portion of the photosensitive resin composition after thermocompression bonding using an alkaline aqueous solution for development; and

[0043] d) a step of heating the developed photosensitive resin film or the developed photosensitive resin composition after thermocompression bonding.

[0044] (12) A semiconductor device comprising the cured product according to (10) arranged as a surface protective film of a semiconductor element or an interlayer insulating film between wiring layers.

[0045] (13) A display device comprising: a first electrode formed on a substrate, an insulating layer formed on the first electrode in a manner that partially exposes the first electrode, and a second electrode arranged opposite to the first electrode, wherein the insulating layer includes the cured product according to (10).

[0046] (14) A display device is a display element including a planarizing film provided in a state of covering the unevenness on a substrate on which a thin film transistor (TFT) is formed, wherein the planarizing film includes the cured product according to (10).

[0047] (15) A method for producing a resin, which is a method for producing one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof and contains a constituent unit represented by formula (1), the method for producing the resin comprising the following steps: allowing hydroxyl groups contained in the structure of one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof to react with a protective agent in a ketone compound represented by (C1) formula (2) and / or a ketone compound represented by (C2) formula (3).

[0048] [Chemistry 5]

[0049]

[0050] (In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 is a monovalent oxymethyl group having 3 to 20 carbon atoms; m represents an integer of 0 to 4, n represents an integer of 1 to 4; * represents a bonding site, and a and b each independently represent an integer of 1 or 2)

[0051] [Chemistry 6]

[0052]

[0053] (In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4 represents a monovalent organic group having 1 to 5 carbon atoms; p represents an integer of 1 or 2; in formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2))

[0054] (16) The method for producing a resin according to (15), wherein the resin is polyimide.

[0055] (17) The method for producing a resin according to (15), wherein an organic acid having a pKa of -2 to 1 is used in the step of reacting with the protecting agent.

[0056] Effects of the Invention

[0057] Since the photosensitive composition of the present invention has high sensitivity, the exposure time can be shortened and the amount of film reduction during development is small. DETAILED DESCRIPTION

[0058] The photosensitive resin composition of the present invention comprises:

[0059] (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof, which contain a structural unit represented by formula (1);

[0060] (B) a photoacid generator; and

[0061] (C) a solvent,

[0062] The (C) solvent includes (C1) a ketone compound represented by the formula (2) and / or (C2) a ketone compound represented by the formula (3).

[0063] [Chemistry 7]

[0064]

[0065] In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 It is a monovalent oxymethyl group having 3 to 20 carbon atoms. m represents an integer of 0 to 4, and n represents an integer of 1 to 4. * represents a bonding site, and a and b each independently represent an integer of 1 or 2.

[0066] [Chemistry 8]

[0067]

[0068] In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4 represents a monovalent organic group having 1 to 5 carbon atoms. p represents an integer of 1 or 2. In formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2).

[0069] The photosensitive resin composition of the present invention contains (B) a photoacid generator, and an acid can be generated in the composition by irradiating exposure light corresponding to the contained photoacid generator. The generated acid can act on R in the polyimide (A) containing the structural unit represented by formula (1). 1 -OR 2 OR in the structure 2 The key between them is converted to R 1 -OH.R 1 -OH functions as a solubility group in alkaline aqueous solution. Therefore, the photosensitive resin composition of the present invention can show a dissolution contrast in alkaline aqueous solution between the unexposed part and the exposed part, so that the exposed part is dissolved to form a relief pattern.

[0070] Therefore, in this specification, R 2 It is called "acid decomposable group". 2 The structure is converted to hydroxyl, so sometimes OR 2 The structure of is called "a hydroxyl group protected by an acid-decomposable group". 1 -OR 2 is converted to R 1 The case of -OH is called "deprotection". 1 -OH reacts with a protecting agent to form R 1 -OH to R 1 -OR 2 The ratio is called the “protection ratio”.

[0071] <(A) One or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof (component (A)) containing a structural unit represented by formula (1)>

[0072] The photosensitive resin composition of the present invention contains (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, which resins contain a structural unit represented by formula (1).

[0073] The so-called polyimide is a polymer containing an imide bond in a repeating unit. The polyimide can be synthesized using a known method. For example, it can be obtained by the following method: for the reaction product obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride or tetracarboxylic diester dichloride, etc. with diamine, corresponding diisocyanate compound or trimethyl silylated diamine, etc., it is dehydrated and ring-closed by heating or reaction using a catalyst such as an acid or base. Therefore, the polyimide has a tetracarboxylic acid and / or its derivative residues, and a diamine and / or its derivative residues.

[0074] The reaction product before dehydration and ring closure is called a polyimide precursor, and the formation of imide bonds by dehydration and ring closure is called imidization. Assuming that the imidization is 100% when curing at 320°C for 1 hour, the ratio of imide structures present in the polyimide and the polyimide precursor is the imidization rate.

[0075] In the present application, the term "polyimide" refers to a polyimide having an imidization rate of 80% or more. From the viewpoint of reducing the amount of outgassing at high temperatures and improving the reliability of a cured product described later, the imidization rate is preferably 90% or more, and more preferably 95% or more.

[0076] As the structure of the component (A) after imidization, it is preferred that the structure unit represented by the formula (7) be included.

[0077] [Chemistry 9]

[0078]

[0079] In formula (7), X1 represents a tetravalent organic group having 4 to 50 carbon atoms, or a constituent unit of formula (1). Y1 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X1 and Y1 is a constituent unit of formula (1), and when X1 is a constituent unit of formula (1), a=b=2, and when Y1 is a constituent unit of formula (1), a+b=2.

[0080] The structure represented by formula (7) has an imide structure having high heat resistance. Therefore, by having the structure represented by formula (7), a photosensitive resin composition having high heat resistance can be formed.

[0081] From the viewpoint of high sensitivity, in the formula (7), X1 is preferably a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. By making X1 in the formula (7) a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms, the hydrophobicity of the resin can be suppressed to a low level, and a resin with high solubility in an alkaline developer can be prepared. Therefore, a good relief pattern with little residue can be formed during exposure and development. Examples of the tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms include the following structures.

[0082] [Chemistry 10]

[0083]

[0084] *Indicates the bonding site.

[0085] From the viewpoint of high sensitivity, when all the tetravalent organic groups represented by X1 are taken as 100 mol %, these are more preferably 50 mol % or more.

[0086] The so-called polybenzoxazole is a polymer containing an oxazole ring in a repeating unit. The polybenzoxazole can be synthesized using a known method. For example, it can be obtained in the following manner: a diamine having a hydroxyl group on the carbon adjacent to the carbon bonded to the nitrogen atom of the amino group (positive position), a corresponding diisocyanate compound or a trimethyl silylated diamine is reacted to obtain a reaction product, and the obtained reaction product is heated to dehydrate and close the ring. Therefore, the polybenzoxazole has a dicarboxylic acid and / or its derivative residues and a dihydroxy diamine and / or its derivative residues.

[0087] The reaction product before dehydration and ring closure is called a polybenzoxazole precursor, and the formation of an oxazole bond by dehydration and ring closure is called oxazolization. The ratio of the oxazole structure present in the polybenzoxazole and the polybenzoxazole precursor is called the oxazolization rate, assuming that the oxazolization is 100% when cured at 320°C for 1 hour.

[0088] In the present application, polybenzoxazole means one having an oxazolylation rate of 80% or more. From the viewpoint of reducing outgassing at high temperatures and improving the reliability of a cured product described later, the oxazolylation rate is preferably 90% or more, more preferably 95% or more.

[0089] The structure of the component (A) after oxazolylation preferably includes a structural unit represented by formula (8).

[0090] [Chemistry 11]

[0091]

[0092] In formula (8), X2 represents a tetravalent organic group having 4 to 50 carbon atoms, or a constituent unit of formula (1). Y2 represents a divalent organic group having 4 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X2 and Y2 is a constituent unit of formula (1), and when X2 is a constituent unit of formula (1), a=b=2, and when Y2 is a constituent unit of formula (1), a+b=2.

[0093] The structure represented by formula (8) has an oxazole structure having high heat resistance. Therefore, by having the structure represented by formula (8), a photosensitive resin composition having high heat resistance can be obtained.

[0094] The so-called polyamide is a polymer containing an amide group in a repeating unit. The polyamide can be synthesized using a known method. For example, it is obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, a dicarboxylic acid diester, a dicarboxylic acid diamide, etc. with a diamine, a corresponding diisocyanate compound or a trimethylsilylated diamine. Therefore, the polyamide has a dicarboxylic acid and / or a derivative residue thereof, and a diamine and / or a derivative residue thereof.

[0095] The structure of the component (A) of the polyamide preferably includes a structural unit represented by formula (9).

[0096] [Chemistry 12]

[0097]

[0098] In formula (9), X3 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of formula (1). Y3 represents a divalent organic group having 4 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X3 and Y3 is a constituent unit of formula (1), and a+b=2.

[0099] In formula (9), X3 is a structure represented by the structural unit of formula (1), and a structure having a hydroxyl group at the normal position relative to the amide group represents a polybenzoxazole precursor structure, and polybenzoxazole is obtained by dehydration ring closure using heat.

[0100] From the viewpoint of high sensitivity, it is preferred that Y2 in the formula (8) and Y3 in the formula (9) are divalent organic groups having 4 to 30 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. By making Y2 in the formula (8) and Y3 in the formula (9) be tetravalent organic groups having 4 to 30 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms, the hydrophobicity of the resin can be suppressed to a low level, and a resin with high solubility in an alkaline developer can be made. Therefore, a good relief pattern with little residue can be formed during exposure and development. Examples of divalent organic groups having 4 to 30 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms include the following structures.

[0101] [Chemistry 13]

[0102]

[0103] *Indicates the bonding site.

[0104] From the viewpoint of high sensitivity, when all the divalent organic groups represented by Y2 and Y3 are taken as 100 mol %, these are more preferably 50 mol % or more.

[0105] The (A) component contained in the photosensitive resin composition of the present invention is preferably sealed at the main chain end by a known end-capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. By sealing the main chain end with an end-capping agent, the storage stability of the photosensitive resin composition can be improved. The introduction ratio of the monoamine used as an end-capping agent is preferably 0.1 mol% or more relative to the total amine components, particularly preferably 5 mol% or more, and preferably 60 mol% or less, particularly preferably 50 mol% or less. The introduction ratio of the anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound used as an end-capping agent is preferably 0.1 mol% or more relative to the diamine component, particularly preferably 5 mol% or more, and preferably 100 mol% or less, particularly preferably 90 mol% or less. Multiple different end groups can be introduced by reacting multiple end-capping agents.

[0106] The weight average molecular weight of component (A) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and still more preferably 7,000 to 60,000 in terms of polystyrene obtained by gel permeation chromatography. By setting the weight average molecular weight to the above range, it is easy to satisfy all of good solvent solubility, good solubility in a developer, and high mechanical strength. In the present invention, the weight average molecular weight is obtained by the method described below.

[0107] From the viewpoint of reducing the film thickness reduction due to heat treatment, it is preferred that the resin (A) containing the structural unit represented by formula (1) contains polyimide. That is, in the photosensitive resin composition of the present invention, it is preferred that the resin (A) contains a polyimide containing the structural unit represented by formula (1).

[0108] The photosensitive resin composition of the present invention contains (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, which resins contain a structural unit represented by formula (1).

[0109] [Chemistry 14]

[0110]

[0111] In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 It is a monovalent oxymethyl group having 3 to 20 carbon atoms. m represents an integer of 0 to 4, and n represents an integer of 1 to 4. * represents a bonding site, and a and b each independently represent an integer of 1 or 2.

[0112] <R 1 Description >

[0113] In formula (1), R 1It is a trivalent to divalent organic group having 3 to 30 carbon atoms. As the trivalent to divalent organic group having 3 to 30 carbon atoms, a known organic group can be used within a range not impairing the effects of the present invention.

[0114] The R 1 It is preferred to have an aromatic ring, and the aromatic ring group and the OH group or OR 2 Direct bonding of the base. 1 Take this structure, OH group or OR 2 The acid dissociation constant (pKa) of the OH group after the deprotection becomes higher, and the alkali solubility is improved. Therefore, it is easy to obtain a relief pattern with less residue. The aromatic ring is preferably a phenyl group or a naphthyl group.

[0115] As R 1 has a phenyl group or a naphthyl group, and the phenyl group or the naphthyl group is OH or OR 2 Specific examples of preferred general formula (1) in which the groups are directly bonded include the following structures.

[0116] [Chemistry 15]

[0117]

[0118] In the structure, R 2 , a and b represent the same meanings as the same symbols in the formula (1). m3, m4, and n3 each independently represent an integer of 0 to 2, and n4 represents an integer of 1 to 2. And m3+m4=m, n3+n4=n, and m and n represent the same meanings as the same symbols in the formula (1).

[0119] In formula (1), m represents an integer of 0 to 4, and n represents an integer of 1 to 4. From the viewpoint of heat resistance of the resin, the value of m+n is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and still more preferably 2.

[0120] In formula (1), * represents a bonding site, and a and b each independently represent an integer of 1 or 2. From the viewpoint of heat resistance of the resin, a=b=1 or a=b=2 is preferred, and a=b=1 is more preferred.

[0121] The structure represented by formula (1) can be obtained, for example, by synthesizing one or more resins selected from the group consisting of the polyimide, polybenzoxazole, polyamide and copolymers thereof using a hydroxyl-containing acid dianhydride or a hydroxyl-containing diamine, and modifying a part or all of the OH groups of the resin to OR 2 base.

[0122] In particular, in the polyamide (A) comprising a structural unit represented by formula (1), when the OH group or OR 2When the group is in the normal position with respect to the nitrogen of the amide group, it is preferably converted into polybenzoxazole by dehydration ring closure by heat, thereby improving heat resistance.

[0123] Examples of the hydroxyl-containing acid dianhydride include 6,6'-methylenebis(5-hydroxyisobenzofuran-1,3-dione), N,N'-(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diyl)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N,N'-(propane-2,2'-diylbis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), and N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), but are not limited thereto.

[0124] Examples of the hydroxyl-containing diamine include 2,4-diaminophenol, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)propane, and bis(3-amino-4-hydroxyphenyl)fluorene, but are not limited thereto.

[0125] From the viewpoint of high sensitivity, the formula (1) is preferably the formula (10).

[0126] [Chemistry 16]

[0127]

[0128] In formula (10), R 2 , a and b represent the same meanings as the same symbols in the formula (1). L represents a direct bond, -C(CH3)2-, 9H-fluorene-1,9-diyl. More preferably, it is -C(CH3)2-, 9H-fluorene-1,9-diyl. m1, m2, n1 and n2 each independently represent an integer of 0 to 2. Among them, 1≦(n1+n2)≦4 is satisfied. * represents a bonding site.

[0129] The 9H-fluorene-1,9-diyl group is a group represented by the following formula.

[0130] [Chemistry 17]

[0131]

[0132] *Indicates the bonding site.

[0133] By converting the above formula (1) into formula (10), R can be reduced 1 -OR 2 Convert to R 1-OH, that is, the activation energy for deprotection. Therefore, a highly sensitive photosensitive resin composition with a high deprotection rate in the exposed part can be prepared. 1 -OR 2 Convert to R 1 -OH, i.e., the activation energy for deprotection.

[0134] <R 2 Description >

[0135] In formula (1), R 2 It is a monovalent oxymethyl group having 3 to 20 carbon atoms. The monovalent oxymethyl group having 3 to 20 carbon atoms is a monovalent group having 3 to 20 carbon atoms having a structure in which carbon and oxygen are bonded in sequence by single bonds from a bonding site. The monovalent oxymethyl group having 3 to 20 carbon atoms can be specifically represented by the following structure.

[0136] [Chemistry 18]

[0137]

[0138] In the structure, R 12 ~R 17 , R 19 represents a monovalent organic group, R 18 and R 20 Indicates a divalent organic group. * indicates a bonding site. The number of carbon atoms in the structure is 3 to 20.

[0139] Examples of the monovalent organic group include an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, and an alkoxycyclic alkyl group having 6 to 16 carbon atoms.

[0140] Examples of the divalent organic group include propane-1,3-diyl, butane-1,3-diyl, pentane-1,3-diyl, or a group in which a hydrogen atom of a group selected from the group consisting of propane-1,3-diyl, butane-1,3-diyl and pentane-1,3-diyl is substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxyalkyl group having 2 to 8 carbon atoms.

[0141] Through the R 2 is a monovalent oxymethyl group having 3 to 20 carbon atoms, and the acid generated in the composition acts on R 1 -OR 2 OR in the structure 2 The key between R 1 -OR 2 Convert to R 1-OH. Therefore, the photosensitive resin composition of the present invention can show a dissolution contrast with respect to an alkaline aqueous solution between an unexposed portion and an exposed portion, so that the exposed portion is dissolved to form a pattern.

[0142] The R 2 Preferably, in formula (1), at least one R 2 is a group represented by formula (11).

[0143] [Chemistry 19]

[0144]

[0145] In formula (11), R 21 R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. 22 and R 23 R represents an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. 24 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. 22 , R 23 and R 24 They can be bonded to each other to form a cyclization. * indicates the bonding site.

[0146] Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.

[0147] Specific examples of the alkoxyalkyl group having 2 to 8 carbon atoms include methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxymethyl, propoxyethyl, propoxypropyl, and propoxybutyl.

[0148] Specific examples of the cyclic alkyl group having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclopentylethyl, cyclohexylethyl, cycloheptylethyl, cyclopentylpropyl, cyclohexylpropyl and cycloheptylpropyl.

[0149] Specific examples of the alkoxycyclic alkyl group having 6 to 16 carbon atoms include methoxypentyl, ethoxypentyl, propoxypentyl, dimethoxypentyl, diethoxypentyl, dipropoxypentyl, trimethoxypentyl, triethoxypentyl, tripropoxypentyl, methoxyhexyl, ethoxyhexyl, propoxyhexyl, dimethoxyhexyl, diethoxyhexyl, dipropoxyhexyl, trimethoxyhexyl, triethoxyhexyl, tripropoxyhexyl, methoxyheptyl, ethoxyheptyl, propoxyheptyl, dimethoxyheptyl, diethoxyheptyl, dipropoxyheptyl, trimethoxyheptyl, triethoxyheptyl, tripropoxyheptyl, and the like.

[0150] Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.

[0151] Formula (11) is R 1 -OR 2 OR in the structure 2 The structure of the α-branch. 2 At least one of them is a group represented by formula (11), which can reduce R 1 -OR 2 Convert to R 1 -OH, that is, the activation energy for deprotection. Therefore, even when a small amount of acid is generated in the photosensitive composition due to exposure, deprotection can be performed, and a highly sensitive photosensitive resin composition can be prepared. Specifically, for R 2 It is preferable to use a group represented by any one of formulae (12) to (14), and it is particularly preferable to use a group represented by formula (14).

[0152] [Chemistry 20]

[0153]

[0154] In formula (12) to formula (14), * represents a bonding site.

[0155] R 1 -OR 2 is by making R 1 For example, by reacting a resin having R -OH with a protective agent in a solvent-free state or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, cyclopentanone, etc., in the presence of an acid or a base at a reaction temperature of -20°C to 50°C. 1 -OH resin reacts with a protective agent to obtain R 1 -OR 2 The resin, namely, the component (A).

[0156] The protecting agent in the present application refers to a compound capable of protecting a hydroxyl group, and the protecting group introduced thereby can be deprotected under the action of an acid or a base. As the protecting agent, a known protecting agent capable of protecting a hydroxyl group can be used.

[0157] As a protective agent, for example in R 2 In the case of 1-ethoxyethyl, ethyl vinyl ether can be used. 2 In the case of 2-tetrahydropyranyl, 3,4-dihydro-2H-pyran and the like can be used.

[0158] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. In addition, organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.

[0159] Examples of the base include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0160] <Fluorine atom content>

[0161] From the viewpoint that the sensitivity change after the photosensitive resin composition is left at room temperature is small, the photosensitive resin composition of the present invention is preferably a photosensitive resin composition in which the fluorine atom content of all the resins is greater than 15% by mass when the total amount of all the resins contained in the photosensitive resin composition is set to 100% by mass. As the fluorine atom content increases, the hydrophobicity increases, and the absorption of water molecules or amines from the surrounding environment after film formation can be avoided, and the change in sensitivity over time can be suppressed.

[0162] The fluorine atom content in all the resins when the total amount of all the resins contained in the photosensitive resin composition is 100% by mass can be analyzed by the following method.

[0163] First, separate the resin from the photosensitive resin composition. Accurately weigh the separated resin as a sample. Use an automatic sample combustion device to burn it in the combustion tube of the analysis device, absorb the generated gas into the solution, and analyze part of the absorption liquid by ion chromatography. As the absorption liquid, H2O2 0.036 mass% can be used.

[0164] <(B) Photoacid generator>

[0165] The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator is a compound having a function of generating an acid by exposure to light. The photoacid generator (B) can be a known one within the range that does not impair the effects of the present invention.

[0166] As the (B) photoacid generator, an onium salt-type ionic photoacid generator or a nonionic photoacid generator can be cited. The so-called onium salt refers to a compound having an electron pair that is not related to a chemical bond, which is generated by a coordination bond with other cationic compounds through the electron pair. In the ionic photoacid generator, the cationic part of the onium salt determines the photochemical properties (molar absorptivity, absorption wavelength, quantum yield), and the anionic part determines the strength of the generated acid. On the other hand, a nonionic photoacid generator is a photoacid generator in which the light-absorbing part is ester-bonded with the acid.

[0167] The ionic photoacid generator is preferably an ionic compound that does not contain heavy metals or halogen ions, and more preferably a triorganic sulfonium salt compound. Specific examples of the triorganic sulfonium salt compound include: triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, perfluoro-1-butanesulfonate ("SP-056", trade name, manufactured by ADEKA); dimethyl-1-naphthylsulfonium sulfonate; dimethyl (4-hydroxy-1-naphthyl) sulfonium sulfonate; dimethyl (4,7-dihydroxy-1-naphthyl) sulfonium sulfonate; diphenyliodonium sulfonate, etc.

[0168] As the nonionic photo-acid generator, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, a sulfonimide compound, a phosphate compound, a sulfonebenzotriazole compound, or the like can be used.

[0169] Specific examples of the diazomethane compound include bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like.

[0170] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred sulfone compounds include 2-(p-toluenesulfonyl)acetophenone, bis(phenylsulfonyl)methane, and the like.

[0171] Specific examples of the sulfonate compound include alkyl sulfonate, halogenated alkyl sulfonate, aryl sulfonate, and iminosulfonate compounds. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenyl sulfonate.

[0172] Specific examples of the carboxylic acid ester compound include 2-nitrobenzyl carboxylate and the like.

[0173] The (B) photoacid generator preferably includes a nonionic photoacid generator. When the (B) photoacid generator includes a nonionic photoacid generator, a photosensitive resin composition with higher sensitivity can be obtained.

[0174] The photoacid generator (B) is more preferably a photoacid generator having an acid dissociation constant (pKa) of -14 to 2 for an acid group generated by light. The photoacid generator can make the acid group generated by light act efficiently on R as an acid by having an acid dissociation constant (pKa) of -14 to 2 for an acid group generated by light in the above range. 1 -OR 2 structure. Therefore, further deprotection can be performed to prepare a highly sensitive photosensitive resin composition. Specific examples of photoacid generators whose acid dissociation constant (pKa) of the acidic group generated by light is in the range of -14 to 2 include photoacid generators whose acid generated by light is trifluoromethanesulfonic acid (pKa = -14), nonafluorobutanesulfonic acid (pKa = -3.57), p-toluenesulfonic acid (pKa = -2.8), methanesulfonic acid (pKa = -2.6), etc.

[0175] The (B) photoacid generator preferably includes an oxime sulfonate compound and / or an imide sulfonate compound. Oxime sulfonate compounds and imide sulfonate compounds are nonionic photoacid generators, and the acidic group generated by light is a sulfonic group, so the acid dissociation constant (pKa) is high, and a photosensitive resin composition with higher sensitivity can be prepared.

[0176] The oxime sulfonate compound can be represented by the following structure.

[0177] [Chemistry 21]

[0178]

[0179] R 25 It is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, trifluoromethanesulfonyl, nonafluorobutyl, perfluorooctyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-yl)methyl, benzyl, phenyl, tosyl, and naphthyl.

[0180] R 26 and R 27 It is a monovalent organic group having 1 to 30 carbon atoms. 26 and R 27Specific examples of the monovalent organic group having 1 to 30 carbon atoms include cyano, trifluoromethyl, hexafluoropropyl, pentafluorobutyl, dodecafluorohexyl, phenyl, 4-methoxyphenyl, 2-fluorenyl, 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl, and the like.

[0181] R 28 It is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the monovalent organic group having 3 to 30 carbon atoms include the following structures.

[0182] [Chemistry 22]

[0183]

[0184] *Indicates the bonding site.

[0185] Specific examples of the oxime sulfonate esters include: "Irgacure" (registered trademark) PAG-103 (benzyl cyanide, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylene), PAG-121 (benzyl cyanide, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylene), PAG-108 (benzyl cyanide, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylene), PAG-203 (all manufactured by BASF, Japan), and PAI-101 ((Z)-4-methoxy-N-(toluenesulfonyloxy)iminobenzyl cyanide, manufactured by Midori Kagaku Co., Ltd.).

[0186] The imidosulfonate compound can be represented by the following structure.

[0187] [Chemistry 23]

[0188]

[0189] R 29 It is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include: 25 The bases listed as specific examples are as follows.

[0190] R 30 and R 31 It is a monovalent organic group having 1 to 30 carbon atoms. 30 and R 31 Specific examples of the monovalent organic group having 1 to 30 carbon atoms include: 26 and R 27The bases listed as specific examples are as follows.

[0191] R 32 It is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the divalent organic group having 3 to 30 carbon atoms include the following structures.

[0192] [Chemistry 24]

[0193]

[0194] R 33 It is a monovalent organic group having 1 to 12 carbon atoms. v represents an integer of 0 to 2. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include methyl, ethyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, 1-(hex-1-en-1-yl) group, and 1-(4-butoxyphenethyl) group. * represents a bonding site.

[0195] Examples of the imide sulfonate compound include N-hydroxynaphthalene imide trifluoromethanesulfonate, "ADEKA ARKLS" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalene imide trifluoromethanesulfonate, manufactured by ADEKA), NA-101 (N-hydroxynaphthalene imide p-toluenesulfonate), and NA-106 (N-hydroxynaphthalene imide camphorsulfonate, all manufactured by Midori Kagaku Co., Ltd.).

[0196] In the present invention, the content of the photoacid generator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of all resins in the photosensitive resin composition. When the photoacid generator (B) is within the above range, a highly sensitive photosensitive resin composition can be obtained.

[0197] <(C) Solvent>

[0198] The photosensitive resin composition of the present invention further comprises a solvent (C). By comprising a solvent, the coating property becomes good and a homogeneous photosensitive resin film can be prepared. From the viewpoint of reducing the film thickness reduction during development, the solvent (C) comprises a ketone compound represented by (C1) formula (2) and / or a ketone compound represented by (C2) formula (3).

[0199] [Chemistry 25]

[0200]

[0201] In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4represents a monovalent organic group having 1 to 5 carbon atoms. p represents an integer of 1 or 2. In formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2).

[0202] Examples of the ketone solvent represented by p=1 in formula (2) include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone (MIBK), 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, etc. As the ketone solvent represented by p=2 in formula (2), in R 3 In the case of a single bond, a diacetyl group may be mentioned, and other examples include acetylacetone and the like.

[0203] Examples of the ketone solvent represented by formula (3) include cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, and 3-methylcycloheptanone.

[0204] From the viewpoint of reducing the film thickness reduction during development, the (C) solvent preferably comprises a ketone compound having a boiling point of 100° C. to 170° C. at standard pressure.

[0205] Furthermore, from the viewpoint of reducing the film thickness reduction during development, the solvent (C) more preferably contains the component (C2), and the component (C2) more preferably contains a ketone compound in the formula (3) wherein q=2 and r=0. That is, the solvent (C) most preferably contains cyclopentanone.

[0206] In the present invention, the content of the solvent (C) is preferably 100 parts by mass or more to dissolve the composition, and is preferably 1,500 parts by mass or less to form a coating film having a thickness of 1 μm or more, based on 100 parts by mass of the component (A).

[0207] As the (C) solvent, a known solvent may be used within a range not impairing the effects of the present invention.

[0208] The (C) solvent used further is not particularly limited, and preferably, an amide solvent, an ester solvent, an alcohol solvent, an ether solvent, a ketone solvent, dimethyl sulfoxide, or the like can be used.

[0209] Specific examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropyleneurea.

[0210] Specific examples of the ester solvent include γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate.

[0211] Specific examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, and the like.

[0212] Specific examples of the ether solvent include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether.

[0213] Specific examples of the ketone solvent include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone (CP), cyclohexanone, cycloheptanone (CH), and dicyclohexyl ketone.

[0214] <Compound represented by formula (4)>

[0215] From the viewpoint of reducing sensitivity changes caused by leaving the composition untreated after exposure, the photosensitive resin composition of the present invention preferably contains the compound represented by formula (4) in an amount of 0.3% by mass or less when the total amount of the photosensitive resin composition is 100% by mass.

[0216] [Chemistry 26]

[0217]

[0218] In formula (4), R 6 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. From the viewpoint of suppressing shrinkage of the film during curing, R 6 Preferred are methyl and ethyl, and more preferred are methyl.

[0219] In formula (4), R 7 R and R are each independently a monovalent organic group having 1 to 12 carbon atoms. From the viewpoint of suppressing shrinkage of the film during curing, 7 Preferred are methyl, ethyl, propyl, isopropyl and butyl, more preferred are methyl and ethyl, and still more preferred is methyl.

[0220] In formula (4), s represents an integer of 2 to 3. From the viewpoint of improving compatibility with the component (A) and suppressing shrinkage of the film during curing, s is preferably 2.

[0221] In formula (4), t represents an integer satisfying 0≦t≦(s+1). From the viewpoint of suppressing shrinkage of the film during curing, t is preferably 0.

[0222] From the viewpoint of reducing sensitivity changes caused by leaving the composition to stand after exposure, the content of the compound represented by formula (4) is more preferably 0.1% by mass or less when the total amount of the photosensitive resin composition is 100% by mass.

[0223] <Compounds represented by formula (5) and formula (6)>

[0224] From the viewpoint of reducing the film thickness reduction during development after the photosensitive resin composition is left at room temperature, the photosensitive resin composition of the present invention preferably further contains a compound represented by formula (5) and / or a compound represented by formula (6), and when the total amount of the photosensitive resin composition is set to 100 mass%, the total content of the compound represented by formula (5) and the compound represented by formula (6) is preferably 0.0001 mass% or more and 0.03 mass% or less.

[0225] [Chemistry 27]

[0226]

[0227] In formula (5), R 8 represents a monovalent organic group having 1 to 6 carbon atoms. From the viewpoint of storage stability of the solution, R 8 Preferred are methyl, ethyl, propyl, isopropyl and butyl, more preferred are methyl and ethyl, and still more preferred is methyl.

[0228] In formula (5), R 9 and R 10 R each independently represents a monovalent organic group having 1 to 3 carbon atoms. 9 and R 10 Preferred is methyl.

[0229] In formula (6), R 11 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. From the viewpoint of storage stability of the solution, R 11 Preferred are a hydrogen atom, a methyl group, an ethyl group, and a propyl group, more preferred are a hydrogen atom and a methyl group, and still more preferred are a hydrogen atom.

[0230] In formula (6), u represents an integer greater than or equal to 0. From the viewpoint of storage stability of the solution, u is preferably an integer of 0 to 3, and more preferably an integer of 0 to 1.

[0231] From the viewpoint of reducing the film thickness reduction during development after the photosensitive resin composition is left at room temperature, when the total amount of the photosensitive resin composition is set to 100% by mass, the total content of the compound represented by formula (5) and the compound represented by formula (6) is more preferably 0.001% by mass or more. In addition, from the same viewpoint, it is more preferably 0.01% by mass or less, and further preferably 0.0035% by mass or less.

[0232] <Organic acid>

[0233] The photosensitive resin composition of the present invention preferably contains an organic acid. From the viewpoint of reducing the sensitivity change after the photosensitive resin composition is left at room temperature, the preferred pKa range of the organic acid is -2 to 1. That is, the photosensitive resin composition of the present invention preferably contains an organic acid having a pKa of -2 to 1. Preferred specific examples include toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, etc., but are not limited to these.

[0234] In order to reduce the sensitivity change after the photosensitive resin composition is left at room temperature, the organic acid is preferably 0.0001 to 0.01 mass %, more preferably 0.0001 to 0.001 mass %, based on 100 mass % of the total amount of the photosensitive resin composition.

[0235] <Other>

[0236] Furthermore, from the viewpoint of stabilizing the structure of the structural unit represented by the formula (1), the photosensitive resin composition of the present invention preferably contains a heterocyclic amine compound. Preferred examples of the heterocyclic amine compound include pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,6-diethylpyridine, 2-n-propylpyridine, 3-n-propylpyridine, 4-n-propylpyridine, 2,6-di-n-propylpyridine, 2-isopropylpyridine, 3-isopropylpyridine, 4-isopropylpyridine, 2,6-diisopropylpyridine, 2-n-butylpyridine, 3-n-butylpyridine, 4-n-butylpyridine, 2,6-di-n-butylpyridine, 2-isobutylpyridine, 3-isobutylpyridine, 4-isobutylpyridine, 2,6-diisobutylpyridine, 2-tert-butylpyridine, 3-tert-butylpyridine, 4-tert-butyl pyridine, 2,6-di-tert-butylpyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, N-methylimidazole, 2-methylimidazole, benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 4-phenylmorpholine, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7-undecene, etc.

[0237] The photosensitive resin composition of the present invention may contain other additives than those described above. Examples of other additives include a dissolution accelerator, a sensitizer, a silane coupling agent, and a surfactant.

[0238] <Hardened material>

[0239] The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.

[0240] As a curing condition, a temperature of 150°C to 320°C is applied to carry out a thermal crosslinking reaction to improve heat resistance and chemical resistance. The heat treatment can be carried out by selecting a temperature and heating it in stages, or by selecting a certain temperature range and carrying out the treatment for 5 minutes to 5 hours while continuously heating it. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. The lower limit of the curing condition in the present invention is preferably above 170°C, but in order to fully carry out the curing, it is more preferably above 170. In addition, the upper limit of the curing condition is preferably below 280°C.

[0241] <Method for producing hardened product (1)>

[0242] The method for producing a hardened product of the present invention comprises:

[0243] (a-1) a step of applying the photosensitive resin composition of the present invention onto a substrate and drying the coating to form a photosensitive resin film;

[0244] (b-1) exposing the photosensitive resin film to light;

[0245] (c-1) a step of washing or removing the exposed portion of the photosensitive resin film after exposure with an alkaline aqueous solution to perform development; and

[0246] (d-1) A step of heat-treating the developed photosensitive resin film.

[0247] The cured product obtained in this manner is mainly composed of polyimide and therefore has excellent heat resistance, electrical insulation, and mechanical properties.

[0248] The method for producing a cured product of the present invention includes the step of applying the photosensitive resin composition of the present invention on a substrate to form a photosensitive resin film.

[0249] The substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafer, ceramic stacked substrate, metal-plated substrate, sapphire, and gallium arsenide.

[0250] The method of coating the photosensitive composition of the present invention on the substrate can be a known method. As the device used for coating, there can be listed: a full coating device such as spin coating, dip coating, curtain coating, spray coating or slit coating, or a printing device such as screen printing, roller coating, micro gravure coating or inkjet.

[0251] After coating, drying is performed to form a photosensitive resin film. Drying is performed using a vacuum drying device or a heating device such as a hot plate or an oven. When a heating device is used, it is preferably performed at a temperature range of 50° C. to 150° C. for 30 seconds to 30 minutes. The film thickness of the photosensitive resin film is preferably 0.1 μm to 100 μm.

[0252] The method for producing a cured product of the present invention includes the step of exposing the photosensitive resin film.

[0253] In the exposure process, exposure is performed on the photosensitive resin film through a mask having a desired pattern. The wavelength of the exposure light irradiated is not particularly limited, and examples thereof include: g-rays (436nm), i-rays (365nm), and h-rays (405nm) with wavelengths of 300nm to 450nm. Among them, it is preferred to irradiate light with a wavelength of 365nm. As light sources used in the exposure process, for example, various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and metal halide lamps can be listed. In addition, as needed, the wavelength of the irradiated light can be adjusted by spectral filters such as long wavelength cutoff filters, short wavelength cutoff filters, and bandpass filters.

[0254] After exposure, post-exposure baking may be performed as required. By performing post-exposure baking, effects such as improved resolution after development or increased allowable range of development conditions can be expected. Post-exposure baking may be performed using an oven, a hot plate, infrared rays, a flash annealing device, a laser annealing device, etc. The post-exposure baking temperature is preferably 50°C to 170°C, more preferably 60°C to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.

[0255] The method for producing a cured product of the present invention includes a step of washing or removing the exposed portion of the photosensitive resin film after exposure with an alkaline aqueous solution to perform development.

[0256] In order to form a pattern of the photosensitive resin composition, after exposure, a developer is used to remove the exposed part. The developer used for development is a solution that dissolves and removes the polymer soluble in the alkaline aqueous solution, typically an alkaline aqueous solution in which an alkaline compound is dissolved. As the alkaline compound, tetramethylammonium hydroxide, potassium hydroxide, sodium carbonate, etc. can be listed. In addition, depending on the circumstances, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc., alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc., or a combination of the above can be added to these alkaline aqueous solutions.

[0257] After development, it is preferred to perform rinsing with an organic solvent or water. When an organic solvent is used, in addition to the developer, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. may also be mentioned. When water is used, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may also be added to water for rinsing.

[0258] The method for producing a cured product of the present invention includes the step of heat-treating the developed photosensitive resin film.

[0259] After development, a temperature of 150°C to 320°C is applied to carry out a thermal crosslinking reaction to improve heat resistance and chemical resistance. The heat treatment is performed by selecting a temperature and heating it in stages, or by selecting a certain temperature range and performing it for 5 minutes to 5 hours while continuously heating it. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. As the lower limit of the curing conditions in the present invention, it is preferably above 170°C, but in order to fully perform the curing, it is more preferably above 180°C. In addition, as the upper limit of the curing conditions, it is preferably below 280°C.

[0260] <Photosensitive resin sheet>

[0261] The shape of the photosensitive resin composition of the present invention is not limited, and may be, for example, a paste or a sheet.

[0262] The photosensitive resin sheet of the present invention is a photosensitive resin sheet obtained by forming the photosensitive resin composition of the present invention into a sheet on a support. The photosensitive resin sheet of the present invention refers to a resin sheet in which the photosensitive resin composition of the present invention is applied to a support and dried at a temperature and for a time within a range in which the solvent can be volatilized, and the photosensitive resin composition of the present invention is in a sheet-like state and is soluble in an organic solvent.

[0263] The support is not particularly limited, and various films commonly available on the market, such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film, can be used. In order to improve adhesion and peelability, surface treatments such as silicone, silane coupling agent, aluminum chelating agent, polyurea, etc. may be applied to the joint surface between the support and the photosensitive resin composition. In addition, the thickness of the support is not particularly limited, and from the perspective of operability, it is preferably in the range of 10 μm to 100 μm. Furthermore, in order to protect the film surface of the photosensitive resin composition obtained by coating, a protective film may also be provided on the film surface. In this way, the surface of the photosensitive resin composition can be protected from pollutants such as dust or dirt in the atmosphere.

[0264] As a method for coating the photosensitive resin composition on the support, there can be cited: spin coating using a spinner, spray coating, roll coating, screen printing, knife coater, die coater, calendar coater, meniscus coater, rod coater, roll coater, notch wheel roll coater, gravure coater, screen coater, slit die coater, etc. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but generally from the viewpoint of uniformity of the coating film, the film thickness after drying is preferably 0.5 μm or more and 100 μm or less.

[0265] An oven, a heating plate, infrared rays, etc. can be used for drying. The drying temperature and drying time can be set within the range that allows the solvent to volatilize, and are preferably set appropriately such that the photosensitive resin composition is in an uncured or semi-cured state. Specifically, it is preferably carried out within the range of 40°C to 150°C for 1 minute to several tens of minutes. In addition, these temperatures can also be combined to increase the temperature in stages, for example, heat treatment can be performed at 80°C and 90°C for 2 minutes each.

[0266] <Method for producing hardened product (2)>

[0267] Another embodiment of the method for producing a cured product of the present invention includes:

[0268] (a-2) using the photosensitive resin sheet of the present invention, the photosensitive resin composition of the present invention is thermally pressed onto a substrate;

[0269] (b-2) exposing the photosensitive resin composition after thermal compression bonding;

[0270] (c-2) a step of washing or removing the exposed portion of the photosensitive resin composition after the exposure and thermocompression bonding with an alkaline aqueous solution to perform development; and

[0271] (d-2) A step of heating the photosensitive resin composition after the development and thermocompression bonding.

[0272] The cured product obtained in this manner is mainly composed of polyimide and therefore has excellent heat resistance, electrical insulation, and mechanical properties.

[0273] The substrate may include silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and substrates having circuit components arranged thereon, but are not limited thereto. Examples of organic circuit substrates include glass-based copper foil laminates such as glass cloth-epoxy copper foil laminates, composite copper foil laminates such as glass nonwoven fabric-epoxy copper foil laminates, heat-resistant-thermoplastic substrates such as polyetherimide substrates, polyetherketone substrates, and polysulfone substrates, and flexible substrates such as polyester copper foil film substrates and polyimide copper foil film substrates. In addition, examples of inorganic circuit substrates include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit constituent materials include: conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low dielectric materials containing glass materials and / or resins, high dielectric materials containing resins or high dielectric constant inorganic particles, insulators containing glass materials, etc.

[0274] The process of laminating the photosensitive resin sheet on the substrate is not particularly limited, and a known method can be used. For example, in the case where the photosensitive resin sheet has a protective film, the support is peeled off while the protective film remains, so that the photosensitive resin composition with the protective film is facing the substrate and bonded by thermocompression. Thermocompression bonding can be performed by hot pressing, hot lamination, hot vacuum lamination, etc. Among them, hot lamination is preferred. In terms of adhesion and embeddability to the substrate, the bonding temperature is preferably above 40°C. In addition, in order to prevent the hardening of the resin composition film during bonding and the deterioration of the resolution of the pattern formed in the exposure / development process, the bonding temperature is preferably below 150°C.

[0275] The steps of exposing the photosensitive resin sheet, developing the exposed portion of the photosensitive resin sheet by washing or removing it with an alkaline aqueous solution, and heating the developed photosensitive resin sheet are not particularly limited and are preferably carried out in the same manner as in the method (1) for producing a cured product.

[0276] <Semiconductor devices>

[0277] The cured product obtained by curing the photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices. The so-called semiconductor device mentioned in the present invention refers to all devices that can function by utilizing the characteristics of semiconductor elements. An electro-optical device or a semiconductor circuit substrate in which a semiconductor element is connected to a substrate, a device in which a plurality of semiconductor elements are stacked, and an electronic device including these are all included in the semiconductor device. In addition, electronic parts such as a multilayer wiring board for connecting semiconductor elements are also included in the semiconductor device. Specifically, it is preferably used for a passivation film of a semiconductor, a surface protection film of a semiconductor element, an interlayer insulating film between a semiconductor element and a rewiring layer, an interlayer insulating film between a plurality of semiconductor elements, an interlayer insulating film between wiring layers of multilayer wiring for high-density mounting, an insulating layer of an organic electric field light-emitting element, etc., but it is not limited thereto and can be used for various purposes.

[0278] The semiconductor device of the present invention is a semiconductor device in which the cured product of the present invention is configured as a surface protective film of a semiconductor element or an interlayer insulating film between wiring layers. By configuring the cured film of the photosensitive composition as a surface protective film of a semiconductor element or an interlayer insulating film between wiring layers, a highly reliable semiconductor device can be produced.

[0279] The semiconductor device of the present invention is preferably a semiconductor device in which the wiring layer and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. By repeatedly arranging the wiring layer and the interlayer insulating film in 2 to 10 layers, the semiconductor device can be miniaturized.

[0280] <Display device>

[0281] The display device of the present invention comprises a first electrode formed on a substrate, an insulating layer formed on the first electrode so as to partially expose the first electrode, and a second electrode arranged opposite to the first electrode, wherein the insulating layer contains the cured product of the present invention.

[0282] Another embodiment of the display device of the present invention is a display device including a planarizing film provided to cover the unevenness on a substrate on which a thin film transistor (TFT) is formed, wherein the planarizing film includes the cured product of the present invention.

[0283] Specifically, it is preferred that the substrate has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode, and the planarization layer and / or the insulating layer contain a display element of the hardened material. If an active matrix display element is taken as an example, a TFT, a wiring located on the side of the TFT and connected to the TFT, is provided on a substrate such as a glass or resin film, and a planarization layer is provided thereon in a manner covering the concave and convex, and a display element is further provided on the planarization layer. The display element and the wiring are connected via contact holes formed on the planarization layer. The hardened material obtained by hardening the photosensitive resin composition of the present invention is preferably provided as a planarization layer in a display device because of its excellent planarization and pattern dimensional stability. In particular, the flexibility of display devices has become mainstream in recent years, and it can also be a display device in which the substrate having the driving circuit contains a resin film.

[0284] <Method for producing polyimide, polybenzoxazole, polyamide and copolymer thereof containing a structural unit represented by formula (1)>

[0285] As a method for producing a resin selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof, which contains a structural unit represented by formula (1), a method for producing a resin having the following steps: reacting a hydroxyl group contained in the structure of one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof with a protective agent in a ketone compound represented by (C1) formula (2) and / or a ketone compound represented by (C2) formula (3). Among them, in the method for producing a resin of the present invention, polyimide is preferred from the viewpoint of the solubility of the resin in the solvent used.

[0286] [Chemistry 28]

[0287]

[0288] In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2It is a monovalent oxymethyl group having 3 to 20 carbon atoms. m represents an integer of 0 to 4, and n represents an integer of 1 to 4. * represents a bonding site, and a and b each independently represent an integer of 1 or 2.

[0289] [Chemistry 29]

[0290]

[0291] In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4 represents a monovalent organic group having 1 to 5 carbon atoms. p represents an integer of 1 or 2. In formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2).

[0292] The so-called protective agent in the present application refers to a compound that can protect a hydroxyl group, and the protective group introduced thereby can be deprotected under the action of an acid or a base. As the protective agent, a known protective agent that can protect a hydroxyl group can be used, and the component (A) containing the constituent unit represented by formula (1) is obtained by reacting the resin with the protective agent. For example, by reacting a resin having R in the absence of a solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, cyclopentanone, in the presence of an acid or a base at a reaction temperature of -20°C to 50°C. 1 The resin having -OH reacts with the protective agent to obtain the component (A) containing the structural unit represented by the formula (1).

[0293] As a protective agent, for example in R 2 In the case of 1-ethoxyethyl, ethyl vinyl ether can be used. 2 In the case of 2-tetrahydropyranyl, 3,4-dihydro-2H-pyran and the like can be used.

[0294] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. In addition, organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.

[0295] Examples of the base include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0296] When the amount of protective agent added is M1 (molar), it is used for R 1 -OH to R 1 -OR 2When the ratio (M2 / M1×100) of the converted amount (M2 mole) is set as the reaction rate (mole %), the reaction rate must be 15 mole %, preferably 20 mole %, more preferably 25 mole %, further preferably 30 mole %, and most preferably 35 mole % or more.

[0297] From the viewpoint of reaction rate, the acid is more preferably an organic acid, and further preferably an organic acid having a pKa of -2 to 1. That is, in the method for producing the resin of the present invention, it is preferred to use an organic acid having a pKa of -2 to 1 in the step of reacting with a protecting agent.

[0298] From the same viewpoint, when the mass of the entire resin before the reaction with the protective agent is set to 100 mass %, the amount of the organic acid added is preferably 0.1 mass % to 1 mass %.

[0299] Examples of the ketone solvent represented by p=1 in formula (2) include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, and 3-penten-2-one. As the ketone solvent represented by p=2 in formula (2), in R 3 In the case of a single bond, a diacetyl group may be mentioned, and other examples include acetylacetone and the like.

[0300] Examples of the ketone solvent represented by formula (3) include cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, and 3-methylcycloheptanone.

[0301] From the viewpoint of further improving the reaction rate, the component (C1) and / or the component (C2) preferably contains a ketone compound having a boiling point of 100°C to 170°C at standard pressure, and more preferably contains the component (C2). It is particularly preferred that cyclopentanone is further contained.

[0302] In the production method of the present invention, a solvent other than (C) may be mixed and used. The solvent used is not particularly limited, and preferably, an amide solvent, an ester solvent, an alcohol solvent, an ether solvent, a ketone solvent, dimethyl sulfoxide, etc. can be used.

[0303] Specific examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropyleneurea.

[0304] Specific examples of the ester solvent include γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate.

[0305] Specific examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, and the like.

[0306] Specific examples of the ether solvent include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether.

[0307] Specific examples of the ketone solvent include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.

[0308] In addition, from the viewpoint of improving the solubility in the component (A) and improving the reaction rate of the protection reaction, the solvent used may be completely distilled off after the reaction with the protecting agent is completed.

[0309] Example

[0310] The present invention will be described in more detail below by way of examples and comparative examples, but the present invention is not limited thereto. In addition, the names of the compounds used using abbreviations are shown below.

[0311] (Acid dianhydride compound)

[0312] TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione

[0313] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

[0314] 6FDA: 4,4'-(hexafluoroisopropylidene) diphthalic anhydride

[0315] (Diamine compound)

[0316] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0317] ABPS: 4,4'-sulfonylbis(2-aminophenol)

[0318] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane

[0319] BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene

[0320] HAB: 3,3'-dihydroxybenzidine

[0321] (acid dicompound)

[0322] ODBC: 4,4'-oxybis(benzoyl chloride)

[0323] BPDC: 4,4'-Dicyclohexyldicarboxylic acid chloride

[0324] (Acid anhydride compound)

[0325] PA: Phthalic anhydride

[0326] ((B) Photoacid generator)

[0327] (Oxime sulfonate compound)

[0328] PAG-103: "Irgacure" (registered trademark) PAG-103 (phenylacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylene, manufactured by BASF Japan)

[0329] ((C)Solvent)

[0330] CP: Cyclopentanone

[0331] CH:Cycloheptanone

[0332] GBL: gamma-butyrolactone

[0333] NMP: N-methylpyrrolidone

[0334] MIBK: 4-Methyl-2-pentanone

[0335] MPA: 3-methoxy-N,N-dimethylpropionamide

[0336] (other)

[0337] IPVE: Isopropyl Vinyl Ether: Protective Agent

[0338] Lutidine: 2,6-Lutidine: A heterocyclic amine compound that stabilizes the structure of the constituent unit represented by formula (1)

[0339] DPA: 3-dimethylamino-N,N-dimethylpropionamide: a compound of the general formula (5).

[0340] (1) Weight average molecular weight of polyimide, polybenzoxazole and polyamide

[0341] The weight average molecular weight (Mw) in terms of polystyrene was measured using a gel permeation chromatography (GPC) analyzer. The weight average molecular weight of polyimide, polybenzoxazole, and polyamide was measured under the following conditions.

[0342] Measurement device: Waters 2695 (manufactured by Waters Corporation)

[0343] Column temperature: 50℃

[0344] Flow rate: 0.4mL / min

[0345] Detector: 2489 UV / Vis detector (Detector) (measurement wavelength 260nm)

[0346] Developing solvent: N-Methylpyrrolidone (NMP) (containing 0.21 wt% lithium chloride and 0.48 wt% phosphoric acid)

[0347] Guard column: TOSOH TSK guard column (manufactured by Tosoh Co., Ltd.)

[0348] Column: TOSOH TSK-GEL a-2500,

[0349] TOSOH TSK-GEL a-4000 series (both manufactured by TOSOH Co., Ltd.).

[0350] (2) Imidization rate (%)

[0351] The polyimide (PI-01 to PI-22) obtained in the synthesis example was dissolved in GBL in a concentration of 35% by mass. The solution was applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 3 minutes to produce a resin film with a thickness of 4μm to 5μm. The wafer with the resin film was divided into two parts, one of which was cured at 140°C for 30 minutes under a nitrogen flow (oxygen concentration of less than 20 volume ppm) using a clean oven (CLH-21CD-S manufactured by KOYO THERMOSYSTEM Co., Ltd.), and then further heated and cured at 320°C for 1 hour to completely close the imide ring (sample IM02). The other part was used directly (sample IM01). The transmission infrared absorption spectra of the resin films (IM01 and IM02) before and after curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak of the imide structure (1,780 cm-1) due to polyimide was confirmed. -1 Nearby, 1,377cm -1 ) and then find the 1,377cm of IM01 -1 The peak intensity near (S), 1,377 cm of IM02 -1 The peak intensity ratio of the peak intensity (S) divided by the peak intensity (T) was calculated as the content of the imide groups in the polyimide before the heat treatment, that is, the imidization ratio.

[0352] (3) Fluorine atom content in all resins in the photosensitive resin composition

[0353] The resin or resin solution is accurately weighed as a sample. The sample is burned in the combustion tube of the analysis device using the automatic sample combustion device described below, and the generated gas is absorbed into the solution, and then part of the absorbed liquid is analyzed by ion chromatography. In the case of a resin solution, the total fluorine atom content (mass %) in the obtained sample is divided by the solid content concentration (%) to obtain the fluorine atom content in the resin.

[0354] <Combustion / Absorption Conditions>

[0355] System: AQF-2100H, GA-210 (Made by Mitsubishi Chemical Corporation)

[0356] Electric furnace temperature: Inlet 900℃ Outlet 1000℃

[0357] Gas: Ar / O2 200mL / min

[0358] :O2 / 400mL / min

[0359] Absorption liquid: H2O2 0.036 mass%, internal standard P 4μg / mL

[0360] Absorption liquid volume: 20mL

[0361] <Ion chromatography / anion analysis conditions>

[0362] System: ICS1600 (manufactured by DIONEX Corporation)

[0363] Mobile phase: 2.7mmol / L Na2CO3 / 0.3mmol / L NaHCO3

[0364] Flow rate: 1.5mL / min

[0365] Detector: Conductivity detector

[0366] Injection volume: 20 μL.

[0367] (4) Protection rate

[0368] The protection rate was measured using a 400MHz, 1H-NMR (Nuclear Magnetic Resonance) device (AL-400 manufactured by JEOL Ltd.). Specifically, the measurement was performed in a deuterated dimethyl sulfoxide solution with a cumulative number of 16 times. The integral value of the protons of the methine (>CH-) derived from the protecting group observed near 5ppm-6ppm and the integral value of the protons of the phenolic hydroxyl group observed near 9ppm-11ppm were calculated, and the ratio of the integral value of the methine protons when the sum of the integral value of the methine protons and the integral value of the protons of the phenolic hydroxyl group was set to 100% was taken as the protection rate (%).

[0369] (5) Solid content concentration

[0370] The solid content concentration is calculated by the following method. 1.500 g of the solution is weighed in an aluminum cup and heated on a hot plate for 30 minutes to evaporate the liquid content. The heating temperature is set to the boiling point of the solvent at standard pressure plus 50 degrees. The weight of the solid content remaining in the aluminum cup after heating is weighed, and the solid content concentration is calculated based on the ratio to the weight before heating.

[0371] (6) Content of the acid compound of the general formula (4) to (6) and having a pKa of -2 to 1

[0372] (6-1) Content in photosensitive resin composition and solvent

[0373] The compositions used in the examples and comparative examples were subjected to GC-MS analysis using a gas chromatography-mass spectrometry (GC-MS) apparatus (manufactured by Agilent) at a column temperature of 40°C to 300°C, a carrier gas of helium (1.5 mL / min), and a scanning range of m / z 29 to 600. The target compounds were subjected to GC-MS analysis under the same conditions as described above, and calibration curves were prepared to calculate the content of the target compound in the photosensitive resin composition and the solvent.

[0374] (6-2) Content in resin powder

[0375] A solution prepared by dissolving 100.0 mg of the resin obtained in Synthesis Example in 1 mL of acetone was subjected to GC-MS analysis in the same manner as described above, and the content of the target compound in the resin powder was calculated.

[0376] (7) Production of embossed patterns

[0377] Using a coating and developing device ACT-8 (manufactured by Tokyo Electron), the photosensitive resin composition obtained from each embodiment and comparative example was applied to an 8-inch silicon wafer by spin coating, and heated at 100°C for 2 minutes to produce a photosensitive resin film with a film thickness of 4.0μm. In addition, the film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings) under the condition of a refractive index of 1.629. Then, using an exposure machine i-ray stepper NSR-2005i9C (manufactured by Nikon), through a mask with a pattern of contact holes of 10μm, at an exposure amount of 5mJ / cm 2 ~300mJ / cm 2 Every 5mJ / cm 2 After exposure, the ACT-8 developing device was used, 2.38 mass % tetramethylammonium hydroxide (TMAH) (manufactured by Tama Chemical Industry Co., Ltd.) was used as a developing solution, and after developing for 80 seconds, it was rinsed with distilled water and spun off to dry to obtain a relief pattern.

[0378] (7-1) Calculation of the amount of reduction in developed film

[0379] The amount of film reduction after development was calculated by subtracting the film thickness after development from the film thickness before development of the unexposed portion. The results were judged as follows, and A with a film reduction of less than 0.7 μm was considered +~B - Set as qualified.

[0380] A + :Development film reduction is less than 0.2μm

[0381] A: The amount of reduction in developed film is 0.2 μm or more and less than 0.3 μm

[0382] A - :The reduction of the developed film is 0.3μm or more and less than 0.4μm

[0383] B + :The reduction of the developed film is 0.4μm or more and less than 0.5μm

[0384] B: The amount of reduction in developed film is 0.5 μm or more and less than 0.6 μm

[0385] B - :The reduction of the developed film is 0.6μm or more and less than 0.7μm

[0386] C: The amount of reduction in developed film is 0.7 μm or more.

[0387] (7-2) Sensitivity

[0388] Regarding sensitivity, the embossed pattern obtained was observed using a flat panel display (FPD) microscope MX61 (manufactured by Olympus) at a magnification of 20 times to measure the opening diameter of the contact hole. The minimum exposure amount at which the opening diameter of the contact hole reached 10 μm was determined and used as the sensitivity. The results were judged as follows, and the sensitivity was less than 200 mJ / cm 2 A + ~B is set as qualified.

[0389] A + : Sensitivity less than 60mJ / cm 2

[0390] A: Sensitivity is 60mJ / cm 2 Above and less than 70mJ / cm 2

[0391] A - : Sensitivity is 70mJ / cm 2 Above and less than 85mJ / cm 2

[0392] B + : Sensitivity is 85mJ / cm 2 Above and less than 100mJ / cm 2

[0393] B: Sensitivity is 100mJ / cm 2 Above and less than 200mJ / cm 2

[0394] C: Sensitivity is 200mJ / cm 2 above.

[0395] (8) Storage stability

[0396] After the photosensitive resin composition obtained in each Example and Comparative Example was left to stand at 23° C. and 45% RH for 5 days, a relief pattern was prepared in the same procedure as in (7).

[0397] (8-1) Calculation of the amount of reduction in developed film

[0398] The same evaluation procedure and criteria as in (7-1) are used to determine whether the product is acceptable or not.

[0399] (8-2) Sensitivity Change

[0400] The sensitivity is calculated using the same evaluation procedure as (7-2). When the sensitivity before placement is set as Eop(B) and the sensitivity after placement is set as Eop(A), the sensitivity change x(%) is calculated using the following formula. The evaluation criteria are determined as follows, and A~B are set as qualified.

[0401] Sensitivity change x (%) = Eop (A) / Eop (B) × 100

[0402] A: x is less than 102

[0403] A - :x is greater than 102 and less than 105

[0404] B + :x is greater than 105 and less than 112

[0405] B: x is greater than 112 and less than 120

[0406] C: x is greater than or equal to 120.

[0407] (9) Effect of storage after exposure

[0408] The photosensitive resin composition obtained from each embodiment and comparative example was used to prepare a relief pattern in the same procedure as (7). At this time, when the sensitivity of the film after exposure is set as Eop (B) when it is developed without being placed, and the sensitivity of the film after exposure is set as Eop (C) when it is developed after being placed in an environment of 23°C and 45% RH for 24 hours, the sensitivity change y (%) is calculated using the following formula, and the evaluation criteria are determined as follows, and A to B are set as qualified.

[0409] Sensitivity change y(%) = Eop(C) / Eop(B)×100

[0410] A: y is less than 110

[0411] B + : y is greater than 110 and less than 150

[0412] B: y is greater than 150 and less than 200

[0413] C: y is 200 or more.

[0414] (10) Changes in film thickness caused by heat treatment

[0415] Using a coating and developing device ACT-8 (manufactured by Tokyo Electron), the photosensitive resin composition obtained from each embodiment and comparative example was applied to an 8-inch silicon wafer by spin coating, and heated at 100°C for 2 minutes to produce a photosensitive resin film with a film thickness of 4.0 μm. In addition, the film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings) under the condition of a refractive index of 1.629. Using a clean oven (CLH-21CD-S manufactured by KOYO THERMO SYSTEM), the wafer with the resin film was heat-treated at 250°C for 30 minutes under a nitrogen flow (oxygen concentration of less than 20 ppm), and the film thickness R (μm) was measured. At this time, the value of R / 4×100 was taken as the film thickness retention rate after heat treatment.

[0416] The evaluation was performed as follows, and A and B having a film thickness retention rate of 70% or more were considered acceptable.

[0417] A: Film thickness retention rate is more than 75%

[0418] B: Film thickness retention rate is 70% or more and less than 75%

[0419] C: The film thickness retention rate is less than 70%.

[0420] Synthesis Example 1 Adjustment of MPA-2

[0421] 1 kg of commercially available MPA (MPA-1) was used to evaluate the content of the compound contained in the general formula (5), and the result showed that it contained 2000 ppm of DPA. Then, MPA-1 was continuously brought into contact with 100 ml of an ion exchange resin (trade name "Amberlyst 16 WET", manufactured by ORGANO (Rohm & Haas)) filled in an ion exchange resin column, and purified until the DPA content reached 800 ppm, thereby obtaining a purified solvent (MPA-2).

[0422] Synthesis Example 2 Adjustment of MPA-3

[0423] 0.4010 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-3) having a DPA content of 2400 ppm.

[0424] Synthesis Example 3 Adjustment of MPA-4

[0425] 4.024 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-4) having a DPA content of 6000 ppm.

[0426] Synthesis Example 4 Adjustment of MPA-5

[0427] 6.048 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-5) having a DPA content of 8000 ppm.

[0428] Synthesis Example 5 Adjustment of MPA-6

[0429] 17.02 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-6) having a DPA content of 18700 ppm.

[0430] Synthesis Example 6 Adjustment of MPA-7

[0431] 19.41 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-7) having a DPA content of 21,000 ppm.

[0432] Synthesis Example 7 Synthesis of polyimide (PI-01)

[0433] Under a dry nitrogen flow, 6FAP 32.96g (90mmol) and NMP 180g as diamines were weighed in a four-necked flask and dissolved. TDA-100 30.03g (100mmol) and NMP 40.00g as dianhydrides were added thereto, and stirred at 40°C for 1 hour. Next, NMP 40.00g and aniline 1.836g (20mmol) as monoamines were added together, reacted at 40°C for 1 hour, and then stirred at 200°C for 4 hours. After stirring, the solution was put into 2L of pure water to obtain a white precipitate. The precipitate was collected by filtration, washed with pure water 3 times, and dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of polyimide (PI-01). The Mw of the obtained resin was 29,600, and the imidization rate was 100%. The content of NMP in the resin powder was 6.5% by mass. The evaluation results are shown in Table 1.

[0434] Synthesis of Synthesis Examples 8 to 18, Synthesis Examples 23 to 28 Polyimide (PI-02 to PI-12, PI-17 to PI-22)

[0435] The synthesis was carried out in the same manner as in Synthesis Example 7 except that the acid dianhydride, monoamine and diamine were changed to the types and amounts described in Table 1 and the polymerization solvent was changed to the type described in Synthesis Example 7. The evaluation results are described in Table 1.

[0436] Synthesis Example 19 Synthesis of polyimide (PI-13)

[0437] The evaluation results are shown in Table 1, except that the white precipitate was collected by filtration and washed 10 times with pure water, a powder of polyimide (PI-13) was obtained in the same manner as in Synthesis Example 1.

[0438] Synthesis Example 20 Synthesis of polyimide (PI-14)

[0439] The white precipitate was collected by filtration and washed 15 times with pure water in the same manner as in Synthesis Example 1 to obtain a powder of a polyimide (PI-14).

[0440] Synthesis Example 21 Synthesis of polyimide (PI-15)

[0441] The evaluation results are shown in Table 1, except that the mixture was dried in a vacuum dryer at 50° C. for 72 hours and then dried in a vacuum dryer at 200° C. for 8 hours.

[0442] Synthesis Example 22 Synthesis of polyimide (PI-16)

[0443] 30.00 g of PI-01 was weighed and dissolved in 120 g of ethyl lactate at room temperature. The liquid was poured into 1 L of pure water to obtain a white precipitate. The precipitate was collected by filtration, washed with pure water three times, and dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of polyimide (PI-16). The evaluation results are recorded in Table 1.

[0444] Synthesis Example 29 Synthesis of polyamide (PA-01)

[0445] Under a dry nitrogen flow, 36.63 g (100 mmol) of 6FAP and 7.405 g (50 mmol) of PA as diamine were dissolved in 75.00 g of NMP in a four-necked flask and stirred at 80°C for 2 hours. Then, the temperature of the solution was cooled to -15°C. After confirming that the temperature of the solution reached -15°C, a solution obtained by dissolving 22.13 g (75 mmol) of ODBC in 30 g of NMP was added dropwise so that the temperature in the reaction system did not exceed 0°C. After the addition was completed, stirring was continued at 20°C for 6 hours. After the reaction was completed, the solution was added to 3 L of pure water containing 10 wt% methanol to precipitate a white precipitate. The precipitate was collected by filtration, washed with pure water 3 times, and dried in a vacuum dryer at 50°C for 72 hours to obtain a polyamide (PA-01). The Mw of the obtained resin was 23,400. The evaluation results are recorded in Table 1.

[0446] Synthesis Examples 30 to 37 Synthesis of polyamides (PA-01 to PA-09)

[0447] The same synthesis as in Synthesis Example 29 was carried out except that the dicarboxylic acid derivative, diamine and terminal anhydride were changed to the types and amounts described in Table 2 and the polymerization solvent was changed to the type described in Table 2. The evaluation results are described in Table 1.

[0448]

[0449]

[0450] Example 1 (A) A polyimide comprising a structural unit represented by formula (1):

[0451] Under a dry nitrogen flow, 10.00 g of PI-01 synthesized in Synthesis Example 7 as a base polymer and 30.00 g of CP as a solvent were weighed and dissolved in a three-necked flask. 0.700 g of IPVE (8.127 × 10 -3 mol), and stirred at 0°C for 1 hour. Then, 1.000×10 trifluoroacetic acid (pKa: 0.23) was added as a catalyst. -2g, stirred at 0°C for 3 hours. After the stirring was completed, the acid catalyst was neutralized with a saturated sodium bicarbonate aqueous solution and the water tank was removed. The organic layer was then washed twice with water. Then, in order to remove the unreacted IPVE, a rotary evaporator was used to remove low-boiling residues. Then, the solid content concentration of the solution was determined, and CP was added in a manner such that the solid content became 40%, and a 40% by mass solution of the solid content of the resin (PI-01-PR10) in which the hydroxyl group was protected by 1-isopropoxyethyl as an acid-decomposable group was obtained. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups (protection rate) was 10 mol%, at which time 36.2 mol% (reaction rate) of IPVE was used for the protection reaction. In addition, the fluorine concentration of the resin was 16.3%. The results are shown in Table 2.

[0452] Example 2 to Example 40 and Comparative Examples 1 to 4

[0453] The synthesis was carried out in the same manner as in Example 1 except that the base polymer type, solvent (type, amount), catalyst (type, pKa, amount), and IPVE amount were changed as shown in Table 2. The results are shown in

[0454] Table 2.

[0455]

[0456]

[0457]

[0458] Synthesis example 38

[0459] PI-01-PR40 (40% CP solution) was concentrated using a rotary evaporator, and after removing the solvent and losing fluidity, the solid content concentration was taken out and measured. CP and CH were added to the solid so that the solid content concentration became 40% and the mass ratio of CP to CH became 5 / 95 to obtain PI-01-PR40CH (40% CH / CP solution).

[0460] Synthesis Example 39

[0461] PI-01-PR40 (40% CP solution) was concentrated using a rotary evaporator, and after the solvent was removed to lose fluidity, the solid content concentration was measured. CP and MIBK were added to the solid so that the solid content concentration became 40% and the mass ratio of CP to MIBK became 5 / 95 to obtain PI-01-PR40M (40% MIBK / CP solution).

[0462] Synthesis Example 40

[0463] 10.00 g of PI-01-PR40 (40% CP solution) was weighed, 6.000 g of GBL was added, and the solvent was replaced using a rotary evaporator. After the solvent replacement, the solid content concentration was measured, and GBL was added so that the solid content concentration became 40%, thereby obtaining PI-01-PR40G (40% GBL solution).

[0464] Synthesis Example 41

[0465] 10.00 g of PI-01-PR40 (40% CP solution) was weighed, 6.000 g of NMP was added, and the solvent was replaced using a rotary evaporator. After the solvent replacement, the solid content concentration was measured, and NMP was added so that the solid content concentration became 40% to obtain PI-01-PR40N (40% NM solution).

[0466] Synthesis Example 42

[0467] 10.00 g of PA-01-PR40 (40% CP solution) was weighed, 6.000 g of GBL was added, and the solvent was replaced using a rotary evaporator. After the solvent replacement, the solid content concentration was measured, and GBL was added so that the solid content concentration became 40%, thereby obtaining PA-01-PR40G (40% GBL solution).

[0468] Synthesis Example 43

[0469] 10.00 g of PA-01-PR40 (40% CP solution) was weighed, 6.000 g of NMP was added, and the solvent was replaced using a rotary evaporator. After the solvent replacement, the solid content concentration was measured, and NMP was added so that the solid content concentration became 40% to obtain PA-01-PR40N (40% NM solution).

[0470] Embodiment 41

[0471] Under a yellow light, 2.500 g of a 40% CP solution of P1-01-PR10 as component (A) and 5.000 × 10 -2 g, 5.000×10-dimethylpyridine as a heterocyclic amine compound that stabilizes the structure of the constituent unit represented by formula (1); -3 g and stirred. Then, 1.500 g of CP was added to adjust the concentration to prepare a photosensitive resin composition. The obtained photosensitive resin composition had an NMP concentration of 1.00% by mass, a total content of general formula (5) and general formula (6) of 0% by mass, and 10×10 trifluoroacetic acid as an organic acid with a pKa of 0.23. -6 The results are shown in Table 3.

[0472] The prepared photosensitive resin composition was subjected to (7) formation of a relief pattern, and evaluations were performed on (7-1) reduction in developed film, (7-2) sensitivity, (8) storage stability, (9) effect of standing after exposure, and (10) film thickness change due to heat treatment. The evaluation results are shown in Table 3.

[0473] Example 42 to Example 80, Comparative Example 5 to Comparative Example 8

[0474] Evaluation was performed in the same manner as in Example 41, except that the formulation of each component of the photosensitive resin composition was changed as described in Table 3. Table 3 shows the evaluation results.

[0475]

[0476]

[0477]

Claims

1. A photosensitive resin composition comprising: (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof, comprising a constituent unit represented by formula (1); (B) a photoacid generator; and (C) a solvent, The solvent (C) comprises (C1) a ketone compound represented by formula (2) and / or (C2) a ketone compound represented by formula (3), [Chemistry 1] (In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 is a monovalent oxymethyl group having 3 to 20 carbon atoms; m represents an integer of 0 to 4, n represents an integer of 1 to 4; * represents a bonding site, and a and b each independently represent an integer of 1 or 2) [Chemistry 2] (In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4 represents a monovalent organic group having 1 to 5 carbon atoms; p represents an integer of 1 or 2; in formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2)).

2. The photosensitive resin composition according to claim 1, wherein The resin (A) contains a polyimide including a structural unit represented by formula (1).

3. The photosensitive resin composition according to claim 1, wherein The component (C1) and / or the component (C2) contains a ketone compound having a boiling point of 100° C. or higher and 170° C. or lower under standard pressure.

4. The photosensitive resin composition according to claim 1, comprising the component (C2), The component (C2) contains a ketone compound wherein q=2 and r=0 in the formula (3).

5. The photosensitive resin composition according to claim 1, wherein Furthermore, when the total amount of the photosensitive resin composition is 100% by mass, the content of the compound represented by formula (4) is 0.3% by mass or less. [Chemistry 3] (In formula (4), R 6 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, R 7 Each independently represents a monovalent organic group having 1 to 12 carbon atoms, s represents an integer of 2 to 3, and t represents an integer satisfying 0≦t≦(s+1)).

6. The photosensitive resin composition according to claim 1, further comprising a compound represented by formula (5) and / or a compound represented by formula (6), When the total amount of the photosensitive resin composition is 100 mass %, the total content of the compound represented by formula (5) and the compound represented by formula (6) is 0.0001% or more and 0.03 mass % or less, [Chemistry 4] (In formula (5), R 8 represents a monovalent organic group having 1 to 6 carbon atoms, R 9 and R 10 Each independently represents a monovalent organic group having 1 to 3 carbon atoms; in formula (6), R 11 represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and u represents an integer greater than 0). 7 . The photosensitive resin composition according to claim 1 , further comprising an organic acid having a pKa of −2 to 1.

8. The photosensitive resin composition according to claim 1, wherein When the total amount of all resins contained in the photosensitive resin composition is 100% by mass, the content of fluorine atoms contained in all the resins is more than 15% by mass. 9 . A photosensitive resin sheet, obtained by forming the photosensitive resin composition according to claim 1 into a sheet on a support. 10 . A cured product obtained by curing the photosensitive resin composition according to claim 1 .

11. A method for manufacturing a hardened object, comprising: a) a step of applying the photosensitive resin composition according to any one of claims 1 to 8 onto a substrate and drying it to form a photosensitive resin film, or a step of thermocompression bonding the photosensitive resin composition of the present invention onto a substrate using the photosensitive resin sheet according to claim 9; b) exposing the photosensitive resin film or the photosensitive resin composition after thermal compression bonding; c) a step of washing or removing the exposed portion of the photosensitive resin film or the exposed portion of the photosensitive resin composition after thermocompression bonding using an alkaline aqueous solution for development; and d) a step of heating the developed photosensitive resin film or the developed photosensitive resin composition after thermocompression bonding.

12. A semiconductor device, wherein the cured product according to claim 10 is arranged as a surface protection film of a semiconductor element or an interlayer insulating film between wiring layers.

13. A display device, comprising: A first electrode formed on a substrate, an insulating layer formed on the first electrode in a manner that the first electrode is partially exposed, and a second electrode disposed opposite to the first electrode, wherein the display device The insulating layer includes the hardener according to claim 10 . 14 . A display device comprising a display element including a planarizing film provided in a state of covering the unevenness on a substrate on which a thin film transistor (TFT) is formed, wherein the planarizing film comprises the cured product according to claim 10 .

15. A method for producing a resin, comprising: reacting a hydroxyl group contained in the structure of the at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof, with a protective agent in a ketone compound represented by (C1) formula (2) and / or a ketone compound represented by (C2) formula (3); [Chemistry 5] (In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 is a monovalent oxymethyl group having 3 to 20 carbon atoms; m represents an integer of 0 to 4, n represents an integer of 1 to 4; * represents a bonding site, and a and b each independently represent an integer of 1 or 2) [Chemistry 6] (In formula (2), R 3 represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, R 4 represents a monovalent organic group having 1 to 5 carbon atoms; p represents an integer of 1 or 2; in formula (3), R 5 represents a monovalent organic group having 1 to 12 carbon atoms, q represents an integer of 1 to 4, and r represents an integer satisfying 0≦r≦(q+2)).

16. The method for producing a resin according to claim 15, wherein: The resin is polyimide.

17. The method for producing a resin according to claim 15, wherein: In the step of reacting with the protecting agent, an organic acid having a pKa of -2 to 1 is used.

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