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

Abstract

The purpose of the present invention is to provide a highly sensitive photosensitive resin composition with which the amount of film reduction during alkaline development is reduced and exposure time can be shortened. The present invention is a photosensitive resin composition comprising (A) one or more kinds of resin including a certain constituent unit, the resin being selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, (B) a photo-acid generator, and (C) a solvent, wherein the (C) solvent includes a (C1) certain ketone compound and / or a (C2) certain ketone compound.

Description

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

[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.

[0002] Polyimides, polybenzoxazoles, and the like, which have excellent heat resistance, electrical insulation properties, and mechanical properties, are widely used in surface protection films and interlayer insulating films used in semiconductor devices, insulating layers in organic electroluminescent devices, and planarizing films for TFT (thin film transistor) substrates. In recent years, photosensitive resin compositions in which these resins themselves or their precursors are given photosensitivity have been used (hereinafter, these photosensitive resin compositions will be referred to as polyimide-based photosensitive resin compositions). The use of polyimide-based photosensitive resin compositions can simplify the pattern processing process and shorten the complicated manufacturing process.

[0003] For polyimide-based photosensitive resin compositions, positive-type materials in which the exposed portions become readily soluble in a developer and can be patterned, and negative-type materials in which the composition itself is readily soluble and the exposed portions become insoluble in a developer, have been proposed. Known polyimide-based photosensitive resin compositions include those in which a quinone diazide compound is added to a polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor (see, for example, Patent Document 1), and those in which a photoacid generator is added to a polyamide containing a protecting group that can be cleaved in the presence of an acid (see, for example, Patent Document 2).

[0004] JP 2011-180473 A JP 2011-221173 A

[0005] In recent years, due to factors such as the increasing size of substrates being used and increased productivity, it has become necessary to shorten the exposure time and to reduce the amount of film loss in unexposed areas during development in order to improve the aperture ratio and in-plane uniformity of film thickness after development.

[0006] The technology described in Patent Document 1 combines an alkali-soluble resin with a quinone diazide compound. The quinone diazide compound interacts with the alkali-soluble resin, reducing the solubility of the composition in an alkaline developer. On the other hand, the quinone diazide compound undergoes a photochemical reaction upon exposure to form an indene carboxylic acid compound, which acts as a dissolution promoter in an alkaline developer. This creates a dissolution contrast between the unexposed and exposed areas, enabling pattern processing. Therefore, sensitivity depends on the amount of quinone diazide compound added. However, increasing the amount of quinone diazide compound reduces the photochemical reaction rate due to the light absorption of the quinone diazide compound itself. Therefore, it is difficult to achieve both a short exposure time and minimal film loss.

[0007] The technology of Patent Document 2 involves substituting the hydrogen atoms of hydroxy groups in an alkali-soluble polyamide with tert-butoxycarbonyl groups (hereinafter also referred to as t-Boc groups) to produce an alkali-insoluble resin, which is then combined with a photoacid generator. This technology generates an acid from the photoacid generator in exposed areas, which reacts with the t-Boc groups, eliminating the t-Boc groups from the polyamide (hereinafter referred to as deprotection), thereby converting the polyamide from alkali-insoluble to alkali-soluble. This creates a dissolution contrast between exposed and unexposed areas, making pattern processing possible. However, this technology suffers from the problem of a low reactivity rate between the t-Boc groups and the acid, making it impossible to shorten the exposure time.

[0008] The present invention is as follows: (1) A photosensitive resin composition comprising: (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, each containing a structural unit represented by formula (1), (B) a photoacid generator, and (C) a solvent, wherein the solvent (C) contains (C1) a ketone compound represented by formula (2) and / or (C2) a ketone compound represented by formula (3).

[0009]

[0010] (In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２is a monovalent oxymethyl group having 3 to 20 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 4. * indicates a bonding site, and a and b each independently represent an integer of 1 or 2.

[0011]

[0012] (In formula (2), R ３ represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, and 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 from 1 to 4, and r represents an integer satisfying 0≦r≦(q+2). (2) The photosensitive resin composition according to (1), wherein the (A) resin comprises a polyimide containing a structural unit represented by formula (1). (3) The photosensitive resin composition according to (1) or (2), wherein the (C1) component and / or the (C2) component comprises 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 any one of (1) to (3), wherein the (C2) component comprises a ketone compound represented by formula (3), in which q = 2 and r = 0. (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.

[0013]

[0014] (In formula (4), R ６ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ７ each independently represent a monovalent organic group having 1 to 12 carbon atoms, s represents an integer of 2 or 3, and t represents an integer satisfying 0≦t≦(s+1). (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), wherein, when the total amount of the photosensitive resin composition is taken as 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.

[0015]

[0016] (In formula (5), R ８ represents a monovalent organic group having 1 to 6 carbon atoms, and R ９ and R １０ each independently represents a monovalent organic group having 1 to 3 carbon atoms. １１represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and u represents an integer of 0 or greater.) (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. (8) The photosensitive resin composition according to any one of (1) to (7), wherein the content of fluorine atoms contained in all resins is greater than 15% by mass, where the total amount of all resins contained in the photosensitive resin composition is taken as 100% by mass. (9) A photosensitive resin sheet obtained by forming the photosensitive resin composition according to any one of (1) to (8) into a sheet shape on a support. (10) A cured product obtained by curing the photosensitive resin composition according to any one of (1) to (8). (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 it to form a photosensitive resin film, or using the photosensitive resin sheet according to (9) to thermocompression bond the photosensitive resin composition of the present invention onto a substrate, b) exposing the photosensitive resin film or the thermocompression-bonded photosensitive resin composition to light, c) developing the exposed portion of the exposed photosensitive resin film or the exposed portion of the exposed and thermocompression-bonded photosensitive resin composition by eluting or removing it with an alkaline aqueous solution, and d) heat-treating the developed photosensitive resin film or the developed thermocompression-bonded photosensitive resin composition. (12) A semiconductor device in which the cured product according to (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 so as to partially expose the first electrode, and a second electrode provided opposite the first electrode, wherein the insulating layer comprises the cured product according to (10). (14) A display device comprising a planarizing film provided in a state of covering irregularities on a substrate on which thin film transistors (TFTs) are formed, wherein the planarizing film comprises the cured product according to (10).(15) A method for producing 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), the method comprising a step of reacting a hydroxyl group contained in the structure of the one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof with a protecting agent in (C1) a ketone compound represented by formula (2) and / or (C2) a ketone compound represented by formula (3).

[0017]

[0018] (In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ is a monovalent oxymethyl group having 3 to 20 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 4. * indicates a bonding site, and a and b each independently represent an integer of 1 or 2.

[0019]

[0020] (In formula (2), R ３ represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, and 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 (15), wherein the resin is a polyimide. (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 protective agent.

[0021] The photosensitive composition of the present invention has high sensitivity, allowing the exposure time to be shortened, and the amount of film loss during development is small.

[0022] The photosensitive resin composition of the present invention comprises: (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, each containing a structural unit represented by formula (1); (B) a photoacid generator; and (C) a solvent, wherein the solvent (C) contains (C1) a ketone compound represented by formula (2) and / or (C2) a ketone compound represented by formula (3).

[0023]

[0024] In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ is a monovalent oxymethyl group having 3 to 20 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 4. * indicates a bonding site, and a and b each independently represent an integer of 1 or 2.

[0025]

[0026] In formula (2), R ３ represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, and 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).

[0027] The photosensitive resin composition of the present invention contains a photoacid generator (B), and thus can generate an acid in the composition by irradiating the composition with exposure light corresponding to the photoacid generator contained therein. The generated acid is reacted with R １ -O-R ２ O-R in the structure ２ It acts on the bond between R １ -OH. １ The —OH group acts as a soluble group in an alkaline aqueous solution, and therefore the photosensitive resin composition of the present invention can exhibit a solubility contrast in an alkaline aqueous solution between the unexposed and exposed areas, allowing the exposed areas to dissolve and form a relief pattern.

[0028] Therefore, in this specification, R ２ is sometimes referred to as an "acid-decomposable group". ２ can be converted to a hydroxyl group by the action of an acid, ２ The structure of R １ -O-R ２ is R １ The conversion of R to —OH is called “deprotection.” １ -OH reacts with the protecting agent to form R １ -OH to R １ -O-R ２ The converted ratio is sometimes called the "protection rate."

[0029] <(A) One or More Resins Selected from the Group Consisting of Polyimides, Polybenzoxazoles, Polyamides, and Copolymers Thereof, Containing a Structural Unit Represented by Formula (1) (Component (A))> The photosensitive resin composition of the present invention contains (A) one or more resins selected from the group consisting of polyimides, polybenzoxazoles, polyamides, and copolymers thereof, containing a structural unit represented by formula (1).

[0030] Polyimides are polymers containing imide bonds in their repeating units. Polyimides can be synthesized by known methods. For example, polyimides can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and then dehydrating and cyclizing the resulting reaction product through heating or a reaction using a catalyst such as an acid or a base. Therefore, polyimides contain residues of tetracarboxylic acid and / or its derivatives, and residues of diamine and / or its derivatives.

[0031] 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. Curing at 320°C for 1 hour was considered to be 100% imidization, and the proportion of imide structures present in the polyimide and the polyimide precursor was taken as the imidization rate.

[0032] In the present application, polyimide refers to one having an imidization rate of 80% or more. From the viewpoints of reducing the amount of outgassing at high temperatures and improving the reliability of the cured product described below, the imidization rate is preferably 90% or more, and more preferably 95% or more.

[0033] The structure of the component (A) after imidization preferably contains a structural unit represented by formula (7).

[0034]

[0035] In formula (7), X １ represents a tetravalent organic group having 4 to 50 carbon atoms or a structural unit of the formula (1). １ represents a divalent organic group having 6 to 30 carbon atoms or a structural unit of the formula (1). １ and Y １ At least one of the structural units is the structural unit of the formula (1), and X １ When the structural unit of the formula (1) is used, a=b=2, and Y １ However, when the structural unit of the formula (1) is used, a+b=2.

[0036] The structure represented by formula (7) has an imide structure with high heat resistance, and therefore, by having the structure represented by formula (7), it is possible to obtain a photosensitive resin composition with high heat resistance.

[0037] From the viewpoint of increasing sensitivity, X in the formula (7) １ is preferably a tetravalent organic group having 4 to 50 carbon atoms and including an aliphatic skeleton having 4 or more carbon atoms. １ However, by being a tetravalent organic group having 4 to 50 carbon atoms and including an aliphatic skeleton having 4 or more carbon atoms, the hydrophobicity of the resin can be kept low, and the resin can be made highly soluble in an alkaline developer. Therefore, a good relief pattern with little residue after exposure and development can be formed. Examples of the tetravalent organic group having 4 to 50 carbon atoms and including an aliphatic skeleton having 4 or more carbon atoms include the following structures:

[0038]

[0039] * indicates the binding site.

[0040] From the viewpoint of high sensitivity, these are X １ It is more preferable that the proportion is 50 mol % or more when all the tetravalent organic groups represented by the following formula are taken as 100 mol %.

[0041] Polybenzoxazole is a polymer containing an oxazole ring in the repeating unit. Polybenzoxazole can be synthesized by known methods. For example, it can be obtained by reacting a dicarboxylic acid, the corresponding dicarboxylic acid dichloride, dicarboxylic acid diester, dicarboxylic acid diamide, etc. with a diamine having a hydroxyl group on the carbon atom adjacent to the nitrogen atom of the amino group (ortho position), the corresponding diisocyanate compound, or trimethylsilylated diamine, and then heating the resulting reaction product to dehydrate and ring-close the reaction product. Therefore, the polybenzoxazole contains residues of dicarboxylic acid and / or its derivatives and residues of dihydroxydiamine and / or its derivatives.

[0042] The reaction product before dehydration and ring closure is called a polybenzoxazole precursor, and the formation of oxazole bonds by dehydration and ring closure is called oxazolization. Curing at 320°C for 1 hour was considered to indicate 100% oxazolization, and based on this, the proportion of oxazole structures present in the polybenzoxazole and the polybenzoxazole precursor was taken as the oxazolization rate.

[0043] In the present application, polybenzoxazole refers to one having an oxazolization rate of 80% or more. From the viewpoints of reducing the amount of outgassing at high temperatures and improving the reliability of the cured product described below, the oxazolization rate is preferably 90% or more, and more preferably 95% or more.

[0044] The structure of component (A) after oxazole conversion preferably contains a structural unit represented by formula (8).

[0045]

[0046] In formula (8), X ２ represents a tetravalent organic group having 4 to 50 carbon atoms or a structural unit of the formula (1). ２represents a divalent organic group having 4 to 30 carbon atoms or a structural unit of the formula (1). ２ and Y ２ At least one of the structural units is the structural unit of the formula (1), and X ２ When the structural unit of the formula (1) is used, a=b=2, and Y ２ However, when the structural unit of the formula (1) is used, a+b=2.

[0047] The structure represented by formula (8) has an oxazole structure with high heat resistance, and therefore, by having the structure represented by formula (8), a photosensitive resin composition with high heat resistance can be obtained.

[0048] Polyamides are polymers containing amide groups in their repeating units. They can be synthesized by known methods. For example, they can be obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, a dicarboxylic acid diester, a dicarboxylic acid diamide, or the like with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. Therefore, the polyamides contain dicarboxylic acid and / or its derivative residues and diamine and / or its derivative residues.

[0049] The structure of the polyamide component (A) preferably contains a structural unit represented by formula (9).

[0050]

[0051] In formula (9), X ３ represents a divalent organic group having 6 to 30 carbon atoms or a structural unit of the formula (1). ３ represents a divalent organic group having 4 to 30 carbon atoms or a structural unit of the formula (1). ３ and Y ３ At least one of the above is a structural unit of the formula (1), and a+b=2.

[0052] In formula (9), X ３ is a structure represented by the structural unit of formula (1) above, and a structure having a hydroxyl group at the ortho position relative to the amide group represents a polybenzoxazole precursor structure, and polybenzoxazole can be obtained by dehydration ring closure by heat.

[0053] From the viewpoint of increasing sensitivity, Y in the formula (8) ２ , Y in the formula (9) ３ is preferably a divalent organic group having 4 to 30 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. ２ , Y in the formula (9) ３ However, by being a tetravalent organic group having 4 to 30 carbon atoms and including an aliphatic skeleton having 4 or more carbon atoms, the hydrophobicity of the resin can be kept low, and the resin can be made highly soluble in an alkaline developer. Therefore, a good relief pattern with little residue after exposure and development can be formed. Examples of divalent organic groups having 4 to 30 carbon atoms and including an aliphatic skeleton having 4 or more carbon atoms include the following structures:

[0054]

[0055] * indicates the binding site.

[0056] From the viewpoint of high sensitivity, these are ２ , Y ３ It is more preferable that the content of the divalent organic groups represented by the formula (I) is 50 mol % or more when all the divalent organic groups represented by the formula (I) are taken as 100 mol %.

[0057] The main chain terminals of the component (A) contained in the photosensitive resin composition of the present invention are preferably capped with a terminal-capping agent such as a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Capping the main chain terminals with the terminal-capping agent can improve the storage stability of the photosensitive resin composition. The proportion of the monoamine used as the terminal-capping agent relative to the total amine components is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 60 mol% or less, and particularly preferably 50 mol% or less. The proportion of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the terminal-capping agent relative to the diamine components is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 100 mol% or less, and particularly preferably 90 mol% or less. Multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0058] The weight-average molecular weight of component (A), as determined by gel permeation chromatography in terms of polystyrene, is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 60,000. By setting the weight-average molecular weight within the above range, it is possible to easily achieve good solvent solubility, good solubility in a developer, and high mechanical strength. In the present invention, the weight-average molecular weight is determined by the method described below.

[0059] From the viewpoint of reducing the film thickness reduction due to heat treatment, the resin (A) containing the structural unit represented by formula (1) preferably contains a polyimide. That is, in the photosensitive resin composition of the present invention, the resin (A) preferably contains a polyimide containing the structural unit represented by formula (1).

[0060] The photosensitive resin composition of the present invention contains one or more resins selected from the group consisting of polyimides, polybenzoxazoles, polyamides, and copolymers thereof, each containing a structural unit represented by formula (1) (A).

[0061]

[0062] In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ is a monovalent oxymethyl group having 3 to 20 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 4. * indicates a bonding site, and a and b each independently represent an integer of 1 or 2.

[0063] <R １ Explanation of Formula (1) １ is a trivalent to dodecavalent organic group having 3 to 30 carbon atoms. Any known trivalent to dodecavalent organic group having 3 to 30 carbon atoms can be used as the trivalent to dodecavalent organic group having 3 to 30 carbon atoms as long as it does not impair the effects of the present invention.

[0064] The R １ has an aromatic ring, and the aromatic ring group is an OH group or an OR group ２ It is preferable that the R １ By adopting such a structure, OH group or OR ２The acid dissociation constant (pKa) of the OH group deprotected from the aromatic ring is increased, and alkali solubility is improved. Therefore, it is easy to obtain a relief pattern with little residue. The aromatic ring is preferably a phenyl group or a naphthyl group.

[0065] R １ has a phenyl group or a naphthyl group, and the phenyl group or the naphthyl group is an OH group or an OR ２ Preferred examples of the general formula (1) directly bonded to the group include the following structures:

[0066]

[0067] In the above structure, R ２ , a, and b have the same meanings as the same symbols in the formula (1). ３ , m ４ , n ３ are each independently an integer of 0 to 2, n ４ represents an integer of 1 or 2. ３ +m ４ = m, n ３ +n ４ = n, and m and n have the same meanings as the same symbols in the formula (1).

[0068] In formula (1), m represents an integer of 0 to 4, and n represents an integer of 1 to 4. From the viewpoint of the heat resistance of the resin, the value of m+n is preferably an integer of 1 to 4, more preferably an integer of 1 or 2, and even more preferably 2.

[0069] In formula (1), * represents a bonding site, and a and b each independently represent an integer of 1 or 2. From the viewpoint of the heat resistance of the resin, it is preferable that a=b=1 or a=b=2, and it is more preferable that a=b=1.

[0070] The structure represented by formula (1) can be obtained by, for example, synthesizing one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof using a hydroxyl group-containing acid dianhydride or a hydroxyl group-containing diamine, and converting some or all of the OH groups of the resin into OR ２ It can be obtained by modifying the group.

[0071] In particular, in polyamides containing a structural unit represented by formula (1) (A), an OH group or an OR group ２ When the group is in the ortho position relative to the nitrogen atom of the amide group, it is converted into polybenzoxazole by thermal dehydration ring closure, which is preferable since it increases the heat resistance.

[0072] Examples of hydroxy group-containing acid dianhydrides include, but are not limited to, 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), N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide).

[0073] Examples of hydroxy group-containing diamines include, but are not limited to, 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.

[0074] From the viewpoint of increasing sensitivity, the formula (1) is preferably the formula (10).

[0075]

[0076] In formula (10), R ２ , a, and b have the same meanings as the same symbols in the formula (1). L is a direct bond, —C(CH ３ ) ２ -, 9H-fluorene-1,9-diyl group. More preferably, -C(CH ３ ) ２ -, 9H-fluorene-1,9-diyl group.１ , m ２ , n １ and n ２ are each independently an integer of 0 to 2, provided that 1≦(n １ +n ２ )≦4. * indicates a binding site.

[0077] The 9H-fluorene-1,9-diyl group is a group represented by the following formula:

[0078]

[0079] * indicates the binding site.

[0080] When the formula (1) is the formula (10), R １ -O-R ２ is R １ This allows the activation energy for conversion to —OH, i.e., deprotection, to be reduced. As a result, a highly sensitive photosensitive resin composition with a high deprotection rate in exposed areas can be obtained. １ -O-R ２ is R １ -OH, that is, the activation energy for deprotection can be reduced. ２ Explanation of Formula (1) ２ 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 and having a structure in which carbon and oxygen are bonded together by a single bond in order from the bonding site. The monovalent oxymethyl group having 3 to 20 carbon atoms can be specifically represented by the following structure:

[0081]

[0082] In the above structure, R １２ ~R １７ , R １９ represents a monovalent organic group, and 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.

[0083] 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.

[0084] Examples of the divalent organic group include a propane-1,3-diyl group, a butane-1,3-diyl group, a pentane-1,3-diyl group, and a group in which a hydrogen atom of a group selected from the group consisting of a propane-1,3-diyl group, a butane-1,3-diyl group, and a pentane-1,3-diyl group has been 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.

[0085] The R ２ is the monovalent oxymethyl group having 3 to 20 carbon atoms, the acid generated in the composition is １ -O-R ２ O-R in the structure ２ It acts on the bond between R １ -O-R ２ R １ Therefore, the photosensitive resin composition of the present invention can exhibit a solubility contrast in an alkaline aqueous solution between the unexposed and exposed areas, and the exposed areas are dissolved to form a pattern.

[0086] The R ２ In formula (1), at least one R ２ is preferably a group represented by formula (11).

[0087]

[0088] In formula (11), R ２１ represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. ２２ and R ２３ 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. ２４represents 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 may be bonded to each other to form a cyclization. * indicates the bonding site.

[0089] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups.

[0090] Specific examples of alkoxyalkyl groups having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, and a propoxybutyl group.

[0091] Specific examples of the cyclic alkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclopentylethyl group, a cyclohexylethyl group, a cycloheptylethyl group, a cyclopentylpropyl group, a cyclohexylpropyl group, and a cycloheptylpropyl group.

[0092] Specific examples of alkoxy cyclic alkyl groups having 6 to 16 carbon atoms include a methoxypentyl group, an ethoxypentyl group, a propoxypentyl group, a dimethoxypentyl group, a diethoxypentyl group, a dipropoxypentyl group, a trimethoxypentyl group, a triethoxypentyl group, a tripropoxypentyl group, a methoxyhexyl group, an ethoxyhexyl group, a propoxyhexyl group, a dimethoxyhexyl group, a diethoxyhexyl group, a dipropoxyhexyl group, a trimethoxyhexyl group, a triethoxyhexyl group, a tripropoxyhexyl group, a methoxyheptyl group, an ethoxyheptyl group, a propoxyheptyl group, a dimethoxyheptyl group, a diethoxyheptyl group, a dipropoxyheptyl group, a trimethoxyheptyl group, a triethoxyheptyl group, and a tripropoxyheptyl group.

[0093] 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 pentoxy group, and a hexoxy group.

[0094] Formula (11) is R １ -O-R ２ O-R in the structure ２ The R ２ At least one of the groups represented by formula (11) is a group represented by formula (11), １ -O-R ２ is R １ Therefore, even if only a small amount of acid is generated in the photosensitive composition upon exposure, deprotection can be achieved, and a highly sensitive photosensitive resin composition can be obtained. ２ A group represented by any one of formulas (12) to (14) is preferably used for the group, and a group represented by formula (14) is particularly preferably used.

[0095]

[0096] In formulas (12) to (14), * represents a binding site.

[0097] R １ -O-R ２ is R １It can be obtained by reacting a resin having —OH with a protecting agent. For example, it can be obtained by reacting a resin having —OH with a protecting agent without solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, or cyclopentanone. １ By reacting a resin having —OH with a protecting agent in the presence of an acid or a base at a reaction temperature of −20 to 50° C., R １ -O-R ２ A resin having the formula (A), i.e., component (A), can be obtained.

[0098] The protecting agent in this application is a compound capable of protecting a hydroxyl group, and the protecting group introduced thereby can be deprotected by 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. For example, R ２ When the alkyl group is a 1-ethoxyethyl group, ethyl vinyl ether can be used, and when the alkyl group is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran, etc. can be used.

[0099] Examples of acids 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. Organic acid salts such as pyridinium p-toluenesulfonate are also preferably used. Examples of bases include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0100] <Fluorine Atom Content> From the viewpoint of minimizing change in sensitivity after leaving the photosensitive resin composition at room temperature, the photosensitive resin composition of the present invention preferably has a fluorine atom content of more than 15% by mass in all resins, where the total amount of all resins contained in the photosensitive resin composition is taken as 100% by mass. As the fluorine atom content increases, hydrophobicity increases, and it is possible to prevent the incorporation of water molecules and amines from the ambient atmosphere after film formation, thereby suppressing change in sensitivity over time.

[0101] The fluorine atom content of all resins in a photosensitive resin composition, when the total amount of all resins contained therein is taken as 100% by mass, can be analyzed by the following method. First, the resin is separated from the photosensitive resin composition. The separated resin is precisely weighed as a sample. Using an automatic sample combustion device, the resin is burned in the combustion tube of an analyzer, and the generated gas is absorbed in a solution. After that, a portion of the absorbed solution is analyzed by ion chromatography. The absorbed solution is H ２ O ２ 0.036% by weight can be used.

[0102] <(B) Photoacid Generator> The photosensitive resin composition of the present invention contains (B) a photoacid generator. A photoacid generator is a compound that has the function of generating an acid upon exposure to light. Any known photoacid generator (B) can be used as long as it does not impair the effects of the present invention.

[0103] Examples of the (B) photoacid generator include onium salt-type ionic photoacid generators and nonionic photoacid generators. An onium salt refers to a compound generated when a compound having an electron pair not involved in a chemical bond forms a coordinate bond with another cationic compound via the electron pair. In the ionic photoacid generator, the cationic portion of the onium salt determines the photochemical properties (molar absorption coefficient, absorption wavelength, quantum yield), and the anionic portion determines the strength of the acid generated. On the other hand, nonionic photoacid generators are photoacid generators in which the light-absorbing portion and the acid are connected via an ester bond.

[0104] The ionic photoacid generator is preferably one that does not contain heavy metals or halogen ions, and is more preferably a triorganosulfonium salt compound. Specific examples of the triorganosulfonium salt compound include triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate ("SP-056", product name, manufactured by ADEKA Corporation); the sulfonate of dimethyl-1-naphthylsulfonium; the sulfonate of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the sulfonate of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the sulfonate of diphenyliodonium.

[0105] As the nonionic photoacid 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.

[0106] Specific examples of diazomethane compounds include bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0107] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred examples of the sulfone compound include 2-(p-toluenesulfonyl)acetophenone, bis(phenylsulfonyl)methane, etc.

[0108] Specific examples of the sulfonate ester compound include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, iminosulfonate ester compounds, etc. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, 2,6-(dinitrobenzyl)phenyl sulfonate, etc.

[0109] Specific examples of carboxylic acid ester compounds include carboxylic acid 2-nitrobenzyl ester.

[0110] The photoacid generator (B) preferably contains a nonionic photoacid generator. By including a nonionic photoacid generator in the photoacid generator (B), a photosensitive resin composition with higher sensitivity can be obtained.

[0111] It is more preferable that the (B) photoacid generator contains a photoacid generator in which the acid dissociation constant (pKa) of the acidic group generated by light is in the range of −14 to 2. When the photoacid generator has the acid dissociation constant (pKa) of the acidic group generated by light in the above range, the acidic group generated by light can be efficiently converted into an acid.１ -O-R ２ As a result, deprotection proceeds more rapidly, resulting in a highly sensitive photosensitive resin composition. Specific examples of the photoacid generator in which the acid dissociation constant (pKa) of the acidic group generated by light is in the range of -14 to 2 include photoacid generators in which the 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), or the like.

[0112] It is more preferable that the photoacid generator (B) contains an oxime sulfonate compound and / or an imide sulfonate compound. The oxime sulfonate compound and the imide sulfonate compound are nonionic photoacid generators, and the acidic group generated by light is a sulfo group, so that the acid dissociation constant (pKa) is high, and a photosensitive resin composition with higher sensitivity can be obtained.

[0113] The oxime sulfonate compound can be represented by the following structure:

[0114]

[0115] R ２５ 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a trifluoromethanesulfonic acid group, a nonafluorobutyl group, a perfluorooctyl group, a (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl group, a benzyl group, a phenyl group, a tosyl group, and a naphthyl group.

[0116] R ２６ and R ２７ is a monovalent organic group having 1 to 30 carbon atoms. ２６ and R ２７may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include a cyano group, a trifluoromethyl group, a hexafluoropropyl group, a pentafluorobutyl group, a dodecafluorohexyl group, a phenyl group, a 4-methoxyphenyl group, a 2-fluorenyl group, and a 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl group.

[0117] R ２８ 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.

[0118]

[0119] * indicates the binding site.

[0120] Specific examples of the oxime sulfonate include "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (benzeneacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (benzeneacetonitrile, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylidene), and PAG-203 (all manufactured by BASF Japan Ltd.), and PAI-101 ((Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Co., Ltd.).

[0121] The imidosulfonate compound can be represented by the following structure:

[0122]

[0123] R ２９ 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 R ２５ Examples of the groups include those given as specific examples of the above.

[0124] R ３０ and R ３１is a monovalent organic group having 1 to 30 carbon atoms. ３０ and R ３１ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include R ２６ and R ２７ Examples of the groups include those given as specific examples of the above.

[0125] R ３２ is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of divalent organic groups having 3 to 30 carbon atoms include the following structures:

[0126]

[0127] R ３３ is a monovalent organic group having 1 to 12 carbon atoms. v is an integer of 0 to 2. Specific examples of monovalent organic groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecanyl group, a 1-(hex-1-en-1-yl) group, and a 1-(4-butoxyphenethyl) group. * indicates a bonding site.

[0128] Examples of the imide sulfonate compound include N-hydroxynaphthalimide triflate, "ADEKA ARCLES" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalimide triflate, manufactured by ADEKA Corporation), NA-101 (N-hydroxynaphthalimide-p-toluenesulfonate), and NA-106 (N-hydroxynaphthalimide camphorsulfonate, all manufactured by Midori Chemical Industry Co., Ltd.).

[0129] In the present invention, the content of (B) the photoacid generator is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of the total resin in the photosensitive resin composition. By setting the content of (B) the photoacid generator in the above range, a highly sensitive photosensitive resin composition can be obtained.

[0130] <(C) Solvent> The photosensitive resin composition of the present invention further contains (C) a solvent. By containing the solvent, the coating property is improved and a homogeneous photosensitive resin film can be formed. From the viewpoint of reducing a decrease in film thickness during development, the (C) solvent contains a ketone compound represented by formula (2) (C1) and / or a ketone compound represented by formula (3) (C2).

[0131]

[0132] In formula (2), R ３ represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, and 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).

[0133] In formula (2), examples of the ketone solvents represented by p=1 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 In formula (2), examples of the ketone solvents represented by p=2 include R ３ When is a single bond, examples include diacetyl, and in other cases examples include acetylacetone.

[0134] 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.

[0135] From the viewpoint of reducing a decrease in film thickness during development, it is preferable that the component (C1) and / or the component (C2) contain a ketone compound having a boiling point of 100°C or higher and 170°C or lower under standard pressure as the solvent (C).

[0136] Furthermore, from the viewpoint of reducing a decrease in film thickness during development, the solvent (C) more preferably contains the component (C2), and the component (C2) further preferably contains a ketone compound represented by formula (3) in which q = 2 and r = 0. That is, the solvent (C) most preferably contains cyclopentanone.

[0137] In the present invention, the content of the (C) solvent is preferably 100 parts by mass or more per 100 parts by mass of the (A) component in order to dissolve the composition, and is preferably 1,500 parts by mass or less in order to form a coating film with a thickness of 1 μm or more.

[0138] As the solvent (C), known solvents can also be used within the range that does not impair the effects of the present invention.

[0139] The solvent (C) to be used is not particularly limited, but suitable examples include amide solvents, ester solvents, alcohol solvents, ether solvents, ketone solvents, and dimethyl sulfoxide.

[0140] Specific examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropylene urea.

[0141] Specific examples of ester solvents 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.

[0142] Specific examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-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-t-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, and propylene glycol.

[0143] Specific examples of ether solvents 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.

[0144] Specific examples of ketone solvents include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone (CP), cyclohexanone, cycloheptanone (CH), and dicyclohexyl ketone.

[0145] <Compound Represented by Formula (4)> From the viewpoint of being able to reduce a change in sensitivity due to standing after exposure, the photosensitive resin composition of the present invention preferably further 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 taken as 100% by mass.

[0146]

[0147] 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 the shrinkage of the film during curing, R ６ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0148] In formula (4), R ７ Each independently represents a monovalent organic group having 1 to 12 carbon atoms. ７ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0149] In formula (4), s represents an integer of 2 or 3. From the viewpoints of improving compatibility with component (A) and suppressing film shrinkage during curing, s is preferably 2.

[0150] In formula (4), t represents an integer that satisfies 0≦t≦(s+1). From the viewpoint of suppressing shrinkage of the film during curing, t is preferably 0.

[0151] From the viewpoint of being able to reduce the change in sensitivity due to standing 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 taken as 100% by mass.

[0152] <Compounds Represented by Formulae (5) and (6)> From the viewpoint of reducing a decrease in film thickness during development after leaving the photosensitive resin composition 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 taken as 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.

[0153]

[0154] 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 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0155] In formula (5), R ９ and R １０ Each independently represents a monovalent organic group having 1 to 3 carbon atoms. ９ and R １０ is preferably a methyl group.

[0156] In formula (6), R １１ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. １１ is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0157] In formula (6), u represents an integer of 0 or more. 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.

[0158] From the viewpoint of reducing a decrease in film thickness during development after leaving the photosensitive resin composition at room temperature, 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, and from the same viewpoint, more preferably 0.01% by mass or less, and even more preferably 0.0035% by mass or less, when the total amount of the photosensitive resin composition is taken as 100% by mass.

[0159] <Organic Acid> The photosensitive resin composition of the present invention preferably contains an organic acid. From the viewpoint of minimizing the change in sensitivity after leaving the photosensitive resin composition at room temperature, the pKa of the organic acid is preferably in the range of -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, and trifluoroacetic acid, but are not limited to these.

[0160] Furthermore, from the viewpoint of minimizing the change in sensitivity after leaving the photosensitive resin composition at room temperature, the organic acid content is preferably 0.0001 to 0.01 mass %, more preferably 0.0001 to 0.001 mass %, when the total amount of the photosensitive resin composition is taken as 100 mass %.

[0161] <Others> Furthermore, from the viewpoint of stabilizing the structure of the constitutional unit represented by 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-normal propylpyridine, 3-normal propylpyridine, 4-normal propylpyridine, 2,6-dinormal propylpyridine, 2-isopropylpyridine, 3-isopropylpyridine, 4-isopropylpyridine, 2,6-diisopropylpyridine, 2-normal butylpyridine, 3-normal butylpyridine, 4-normal butylpyridine, 2,6-dinormal butylpyridine, 2-isobutylpyridine, 3-isobutylpyridine, 4-isobutylpyridine, 2,6-diisobutylpyridine, 2-tert-butylpyridine, 3-tert-butylpyridine, 4-tert- butylpyridine, 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-oxyquinoline, 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, and the like.

[0162] The photosensitive resin composition of the present invention may contain other additives in addition to those described above, such as a dissolution promoter, a sensitizer, a silane coupling agent, a surfactant, etc.

[0163] <Cured Product> The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.

[0164] As for the curing conditions, a temperature of 150°C to 320°C is applied to promote the thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment can be carried out by selecting a temperature and increasing the temperature stepwise, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but 170°C or higher is more preferable in order to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0165] <Method for Producing Cured Product (1)> The method for producing a cured product of the present invention includes: (a-1) a step of applying the photosensitive resin composition of the present invention onto a substrate and drying it to form a photosensitive resin film; (b-1) a step of exposing the photosensitive resin film to light; (c-1) a step of developing the exposed portion of the exposed photosensitive resin film by dissolving or removing it with an alkaline aqueous solution; and (d-1) a step of heat-treating the developed photosensitive resin film.

[0166] The cured product obtained in this manner is a cured product mainly composed of polyimide, and therefore has excellent heat resistance, electrical insulation properties, and mechanical properties.

[0167] The method for producing a cured product of the present invention includes a step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin film.

[0168] The substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafer, ceramic deposition substrate, metal plated substrate, sapphire, and gallium arsenide.

[0169] The photosensitive composition of the present invention can be applied to a substrate by any known method, including, for example, a full-surface coating apparatus such as spin coating, dip coating, curtain flow coating, spray coating, or slit coating, or a printing apparatus such as screen printing, roll coating, microgravure coating, or inkjet printing.

[0170] After coating, the coating is dried to form a photosensitive resin film. Drying is performed using a vacuum dryer or a heating device such as a hot plate or oven. When using a heating device, drying is preferably performed at a temperature of 50 to 150°C for 30 seconds to 30 minutes. The thickness of the photosensitive resin film is preferably 0.1 to 100 μm.

[0171] The method for producing a cured product of the present invention includes a step of exposing the photosensitive resin film to light.

[0172] In the exposure step, the photosensitive resin film is exposed through a mask having a desired pattern. The wavelength of the exposure light to be irradiated is not particularly limited, and examples thereof include light having a wavelength of 300 to 450 nm, such as g-line (436 nm), i-line (365 nm), and h-line (405 nm). Of these, light having a wavelength of 365 nm is preferred. Examples of light sources used in the exposure step include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, and metal halide lamps. Furthermore, the wavelength of the irradiated light may be adjusted, if necessary, through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a bandpass filter.

[0173] After exposure, post-exposure baking may be performed as necessary. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance for development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like can be used. The post-exposure baking temperature is preferably 50 to 170°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.

[0174] The method for producing a cured product of the present invention includes a step of developing the exposed portion of the photosensitive resin film by dissolving or removing it with an alkaline aqueous solution.

[0175] To form a pattern of the photosensitive resin composition, after exposure, the exposed area is removed using a developer. The developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution containing an alkaline compound dissolved therein. Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added, either alone or in combination, to these alkaline aqueous solutions.

[0176] After development, it is preferable to perform a rinse treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, examples of the solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may also be added to the water for rinsing treatment.

[0177] The method for producing a cured product of the present invention includes a step of heat-treating the developed photosensitive resin film.

[0178] After development, a temperature of 150°C to 320°C is applied to promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0179] <Photosensitive Resin Sheet> The photosensitive resin composition of the present invention is not limited in shape, and may be in the form of, for example, a paste or a sheet.

[0180] 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 shape on a support. The photosensitive resin sheet of the present invention refers to a sheet-like product obtained by applying the photosensitive resin composition of the present invention onto a support and drying it at a temperature and for a time within a range that allows the solvent to volatilize, resulting in a photosensitive resin composition of the present invention that is not completely cured and is soluble in an organic solvent.

[0181] The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the photosensitive resin composition may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and peelability. The thickness of the support is also not particularly limited, but from the viewpoint of workability, a thickness of 10 to 100 μm is preferable. Furthermore, to protect the surface of the photosensitive resin composition film obtained by coating, a protective film may be provided on the film surface. This protects the surface of the photosensitive resin composition from contaminants such as dust and dirt in the atmosphere.

[0182] Examples of methods for applying the photosensitive resin composition to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and methods using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The coating film thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity, etc.

[0183] For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and drying time may be within a range that allows the solvent to volatilize, and it is preferable to appropriately set a range that allows the photosensitive resin composition to be in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 40°C to 150°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 80°C and 90°C for 2 minutes each.

[0184] <Method for producing a cured product (2)> Another embodiment of the method for producing a cured product of the present invention includes: (a-2) a step of thermocompression-bonding the photosensitive resin composition of the present invention onto a substrate using the photosensitive resin sheet of the present invention; (b-2) a step of exposing the thermocompression-bonded photosensitive resin composition; (c-2) a step of developing the exposed portion of the exposed, thermocompression-bonded photosensitive resin composition by eluting or removing it with an alkaline aqueous solution; and (d-2) a step of heat-treating the developed, thermocompression-bonded photosensitive resin composition.

[0185] The cured product obtained in this manner is a cured product mainly composed of polyimide, and therefore has excellent heat resistance, electrical insulation properties, and mechanical properties.

[0186] Examples of the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and circuit components disposed on these substrates. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth / epoxy copper-clad laminates, heat-resistant thermoplastic substrates such as polyetherimide substrates, polyetherketone substrates, and polysulfone substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards 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 components include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low-dielectric materials containing glass-based materials and / or resins; high-dielectric materials containing resins or high-dielectric-constant inorganic particles; and insulators containing glass-based materials.

[0187] The process of laminating the photosensitive resin sheet onto the substrate is not particularly limited, and known methods can be used. For example, when the photosensitive resin sheet has a protective film, the support is peeled off while leaving the protective film, and the photosensitive resin composition with the protective film is placed face-to-face with the substrate and bonded by thermocompression bonding. Thermocompression bonding can be performed by heat pressing, thermal lamination, thermal vacuum lamination, etc. Among these, thermal lamination is preferred. The bonding temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, the bonding temperature is preferably 150°C or lower to prevent the resin composition film from curing during bonding, which would deteriorate the resolution of pattern formation in the exposure and development steps.

[0188] There are no particular restrictions on the step of exposing the photosensitive resin sheet to light, the step of developing the exposed portion of the exposed photosensitive resin sheet by dissolving or removing it with an alkaline aqueous solution, and the step of heat-treating the developed photosensitive resin sheet, but it is preferable that these steps be carried out in the same manner as in the method (1) for producing a cured product.

[0189] <Semiconductor Device> The cured product obtained by curing the photosensitive resin composition of the present invention can be used in electronic components such as semiconductor devices. In the present invention, the term "semiconductor device" refers to any device that can function by utilizing the characteristics of a semiconductor element. Semiconductor devices include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these. Semiconductor devices also include electronic components such as multilayer wiring boards for connecting semiconductor elements. Specifically, the cured product is suitable for applications such as a passivation film for semiconductors, a surface protection film for semiconductor elements, an interlayer insulating film between a semiconductor element and a rewiring layer, an interlayer insulating film between multiple semiconductor elements, an interlayer insulating film between wiring layers in multilayer wiring for high-density packaging, and an insulating layer for organic electroluminescent elements, but is not limited thereto and can be used for a variety of applications.

[0190] The semiconductor device of the present invention is a semiconductor device in which the cured product of the present invention is disposed as a surface protective film for a semiconductor element or an interlayer insulating film between wiring layers. By disposing a cured film of the photosensitive composition as a surface protective film for a semiconductor element or an interlayer insulating film between wiring layers, a highly reliable semiconductor device can be obtained.

[0191] 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.

[0192] <Display Device> The display device of the present invention is a display device including 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 provided opposite the first electrode, wherein the insulating layer includes the cured product of the present invention.

[0193] Another embodiment of the display device of the present invention is a display element comprising a planarization film provided in a state of covering irregularities on a substrate on which thin film transistors (TFTs) are formed, wherein the planarization film comprises the cured product of the present invention.

[0194] Specifically, the display device preferably has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, with the planarization layer and / or insulating layer containing the cured product. Taking an active matrix display device as an example, a display device may have a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or a resin film, a planarization layer disposed thereon to cover the irregularities, and a display device further disposed on the planarization layer. The display device and the wiring are connected via contact holes formed in the planarization layer. The cured product obtained by curing the photosensitive resin composition of the present invention has excellent planarization properties and pattern dimensional stability, and is therefore preferably provided as a planarization layer in a display device. In particular, flexible display devices have become mainstream in recent years, and the display device may have a substrate having the driving circuit described above made of a resin film.

[0195] <Method for producing polyimide, polybenzoxazole, polyamide, and copolymers thereof containing a structural unit represented by formula (1)> As a method for producing one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof containing a structural unit represented by formula (1), a preferred method for producing a resin includes a step of reacting hydroxyl groups contained in the structure of one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof with a protecting agent in a ketone compound represented by formula (2) (C1) and / or a ketone compound represented by formula (3) (C2). In particular, the resin production method of the present invention is preferably for polyimide from the viewpoint of the solubility of the resin in the solvent used.

[0196]

[0197] In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ is a monovalent oxymethyl group having 3 to 20 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 4. * indicates a bonding site, and a and b each independently represent an integer of 1 or 2.

[0198]

[0199] In formula (2), R ３ represents a single bond or a monovalent or divalent organic group having 1 to 12 carbon atoms, and 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).

[0200] The protecting agent in this application is a compound capable of protecting a hydroxyl group, and the protecting group introduced thereby can be deprotected by the action of an acid or a base. A known protecting agent capable of protecting a hydroxyl group can be used as the protecting agent, and the component (A) containing the structural unit represented by formula (1) can be obtained by reacting the resin with the protecting agent. For example, the component (A) containing the structural unit represented by formula (1) can be obtained by reacting the resin with the protecting agent without a solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, or cyclopentanone. １ The component (A) containing the structural unit represented by formula (1) can be obtained by reacting a resin having an —OH group with a protecting agent in the presence of an acid or a base at a reaction temperature of −20 to 50° C.

[0201] Examples of the protecting agent include R ２ When the alkyl group is a 1-ethoxyethyl group, ethyl vinyl ether can be used, and when the alkyl group is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran, etc. can be used.

[0202] 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. Organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.

[0203] Examples of the base include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0204] Amount of protective agent added M1 (mol) of which R １ -OH to R １ -O-R ２When the ratio (M2 / M1 × 100) of the amount (M2 moles) used for the conversion of M2 is taken as the reaction rate (mol %), the reaction rate must be 15 mol %, preferably 20 mol %, more preferably 25 mol %, even more preferably 30 mol %, and most preferably 35 mol % or more.

[0205] From the viewpoint of the reaction rate, the acid is more preferably an organic acid, and even more preferably an organic acid having a pKa of −2 to 1. That is, in the method for producing a resin of the present invention, an organic acid having a pKa of −2 to 1 is preferably used in the step of reacting with a protecting agent.

[0206] From the same viewpoint, the amount of organic acid added is preferably 0.1 to 1% by mass when the mass of the entire resin before reaction with the protective agent is taken as 100% by mass.

[0207] In formula (2), examples of the ketone solvent represented by p=1 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, and 3-hexanone. Examples of the ketone solvents represented by formula (2) where p=2 include 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. ３ When is a single bond, examples include diacetyl, and in other cases examples include acetylacetone.

[0208] 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.

[0209] Furthermore, from the viewpoint of improving the reaction rate, the component (C1) and / or the component (C2) preferably contains a ketone compound having a boiling point under standard pressure of 100° C. or higher and 170° C. or lower, and more preferably contains the component (C2). Furthermore, it is particularly preferable that the component (C2) contains cyclopentanone.

[0210] In the production method of the present invention, a solvent other than (C) may be mixed and used. The solvent to be used is not particularly limited, but amide-based solvents, ester-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, dimethyl sulfoxide, etc. can be suitably used.

[0211] Specific examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropylene urea.

[0212] Specific examples of ester solvents 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.

[0213] Specific examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-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-t-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, and propylene glycol.

[0214] Specific examples of ether solvents 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.

[0215] Specific examples of ketone solvents include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.

[0216] From the viewpoint of improving the solubility of the component (A) and improving the reaction rate of the protection reaction, the solvent used may be completely removed by distillation after completion of the reaction with the protecting agent.

[0217] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The names of the compounds used, for which abbreviations are used, are shown below.

[0218] (Acid dianhydride compounds) TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (Diamine compounds) 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane ABPS: 4,4'-sulfonylbis(2-aminophenol) BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene HAB: 3,3'-dihydroxybenzidine (Acid dianhydride compounds) ODBC: 4,4'-oxybis(benzoyl chloride) BPDC: 4,4'-dicyclohexyldicarboxylic acid chloride (acid anhydride compound) PA: phthalic anhydride ((B) photoacid generator) (oxime sulfonate compound) PAG-103: "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene, manufactured by BASF Japan Ltd.) ((C) solvent) CP: cyclopentanone CH: cycloheptanone GBL: γ-butyrolactone NMP: N-methylpyrrolidone MIBK: 4-methyl-2-pentanone MPA: 3-methoxy-N,N-dimethylpropanamide (others) IPVE: isopropyl vinyl ether: protective agent Lutidine: 2,6-lutidine: a heterocyclic amine compound that stabilizes the structure of the structural unit represented by formula (1). DPA: 3-dimethylamino-N,N-dimethylpropionamide: a compound of general formula (5).

[0219] (1) Weight-average molecular weight of polyimide, polybenzoxazole, and polyamide The weight-average molecular weight (Mw) in terms of polystyrene was measured using a GPC analyzer. The weight-average molecular weight of polyimide, polybenzoxazole, and polyamide was measured under the following conditions. Measurement device: Waters 2695 (manufactured by Waters Corporation) Column temperature: 50°C Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21 wt% lithium chloride and 0.48 wt% phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).

[0220] (2) Imidization Rate (%) The polyimides (PI-01 to PI-22) obtained in the synthesis examples were dissolved in GBL to a concentration of 35% by mass. This 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 4 to 5 μm thick. This resin-coated wafer was divided into two, and one was cured in a clean oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 20 ppm by volume or less) at 140°C for 30 minutes, then further heated to 320°C for 1 hour to completely close the imide ring (Sample IM02). The other was used as is (Sample IM01). The transmission infrared absorption spectra of the resin films (IM01, IM02) before and after curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak (1,780 cm ) of the imide structure due to polyimide was observed. －１ Near 1,377 cm －１ After confirming the existence of the 1,377 cm －１ Peak intensity (S) near 1,377 cm of IM02 －１ The peak intensity ratio was calculated by dividing the peak intensity (S) by the peak intensity (T), and this was taken as the content of imide groups in the polyimide before heat treatment, i.e., the imidization rate.

[0221] (3) Fluorine Atom Content in Total Resin in Photosensitive Resin Composition A resin or resin solution was precisely weighed as a sample. Using the automatic sample combustion apparatus described below, the resin or resin solution was burned in the combustion tube of an analyzer, and the generated gas was absorbed into a solution. A portion of the absorbed solution was then analyzed by ion chromatography. In the case of a resin solution, the total fluorine atom content (% by mass) in the obtained sample was divided by the solid content (%) to determine the fluorine atom content in the resin.

[0222] <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C Outlet 1000°C Gas: Ar / O ２ 200mL / min :O ２ / 400 mL / min Absorption liquid: H ２ O ２ 0.036 mass%, internal standard P 4 μg / mL Amount of absorption solution: 20 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DINONEX Co., Ltd.) Mobile phase: 2.7 mmol / L Na ２ CO ３ / 0.3 mmol / L NaHCO ３ Flow rate: 1.5 mL / min. Detector: electrical conductivity detector. Injection volume: 20 μL.

[0223] (4) Protection Rate The protection rate was measured using a 400 MHz, 1H-NMR (nuclear magnetic resonance) spectrometer (AL-400 manufactured by JEOL Ltd.). Specifically, the measurement was performed in a deuterated dimethyl sulfoxide solution with 16 integrations. The integral value of the proton of the methine group (>CH-) derived from the protecting group observed around 5-6 ppm and the integral value of the proton of the phenolic hydroxyl group observed around 9-11 ppm were calculated, and the ratio of the integral value of the proton of the methine group to the integral value of the proton of the phenolic hydroxyl group, when the sum of the integral values ​​of the protons of the methine group and the protons of the phenolic hydroxyl group was taken as 100%, was defined as the protection rate (%).

[0224] (5) Solid Content Concentration The solid content concentration was determined by the following method. 1,500 g of the solution was weighed into an aluminum cup and heated on a hot plate for 30 minutes to evaporate the liquid. The heating temperature was set to a value obtained by adding 50 degrees to the boiling point of the solvent under standard pressure. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration was determined from the ratio to the weight before heating.

[0225] (6) Content of general formulas (4) to (6) and acid compounds having a pKa of -2 to 1 (6-1) Content in photosensitive resin composition and solvent The compositions used in each example and comparative example were subjected to GC-MS analysis using a GC-MS device (manufactured by Agilent) under the following conditions: column temperature: 40 to 300°C, carrier gas: helium (1.5 mL / min), scan range: m / z 29 to 600. Each target compound was subjected to GC-MS analysis under the same conditions as above to create a calibration curve, and the content of the target compound in the photosensitive resin composition and solvent was calculated.

[0226] (6-2) Content in Resin Powder A solution obtained 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.

[0227] (7) Preparation of Relief Pattern The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied by spin coating onto an 8-inch silicon wafer using an ACT-8 coater / developer (manufactured by Tokyo Electron Limited), and heated at 100°C for 2 minutes to prepare a photosensitive resin film with a film thickness of 4.0 μm. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. Thereafter, using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), the film was exposed to light at an exposure dose of 5 to 300 mJ / cm through a mask having a pattern of 10 μm contact holes. ２ in the range of 5 mJ / cm ２After the exposure, the film was developed for 80 seconds using the ACT-8 developing device with 2.38% by mass of TMAH (manufactured by Tama Chemicals Co., Ltd.) as a developer, and then rinsed with distilled water and spun off to dry, thereby obtaining a relief pattern.

[0228] (7-1) Calculation of the amount of film loss after development The amount of film loss after development was calculated by subtracting the film thickness after development from the film thickness before development in the unexposed area. The results were evaluated as follows. ＋ ~B － The result was a pass. ＋ A: The amount of reduction in the developed film is less than 0.2 μm. A: The amount of reduction in the developed film is 0.2 μm or more and less than 0.3 μm. － B: The amount of reduction in the developed film is 0.3 μm or more and less than 0.4 μm ＋ B: The amount of reduction in the developed film is 0.4 μm or more and less than 0.5 μm. B: The amount of reduction in the developed film is 0.5 μm or more and less than 0.6 μm. － : The amount of reduction in the developed film is 0.6 μm or more and less than 0.7 μm. C: The amount of reduction in the developed film is 0.7 μm or more.

[0229] (7-2) Sensitivity The resulting relief pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the sensitivity. The results were judged as follows, and a sensitivity of 200 mJ / cm was determined. ２ Less than A ＋ ~B was considered a pass. ＋ : Sensitivity is 60 mJ / cm ２ A: Sensitivity is less than 60 mJ / cm ２ 70mJ / cm or more ２ Less than A － : Sensitivity is 70 mJ / cm ２ 85mJ / cm or more ２ Less than B ＋ : Sensitivity is 85 mJ / cm ２ More than 100mJ / cm ２ B: Sensitivity is less than 100 mJ / cm ２ More than 200mJ / cm ２ C: Sensitivity is less than 200 mJ / cm ２ That's all.

[0230] (8) Storage Stability The photosensitive resin compositions obtained in the examples and comparative examples were allowed to stand at 23° C. and 45% RH for 5 days, and then a relief pattern was formed on each of the compositions in the same manner as in (7).

[0231] (8-1) Calculation of the Amount of Developed Film Reduced The pass / fail judgment was made according to the same evaluation procedure and criteria as in (7-1).

[0232] (8-2) Sensitivity Change Sensitivity was determined using the same evaluation procedure as in (7-2). When the sensitivity before standing was Eop(B) and the sensitivity after standing was Eop(A), the sensitivity change x (%) was calculated using the following formula, and the evaluation criteria were set as follows, with A to B being considered acceptable. Sensitivity change x (%) = Eop(A) / Eop(B) x 100 A: x is less than 102 A － : x is 102 or more and less than 105 B ＋ : x is 105 or more and less than 112 B: x is 112 or more and less than 120 C: x is 120 or more.

[0233] (9) Effect of leaving after exposure A relief pattern was prepared using the photosensitive resin composition obtained in each Example and Comparative Example in the same procedure as in (7). In this case, assuming that the sensitivity when the exposed film was developed without leaving it, and the sensitivity when the exposed film was left for 24 hours in an environment of 23°C and 45% RH and then developed, is Eop(B), the sensitivity change y(%) was calculated using the following formula, and the evaluation criteria were set as follows, with A to B being considered as passing. Sensitivity change y(%)=Eop(C) / Eop(B)×100 A: y is less than 110 B: ＋ A: y is 110 or more and less than 150 B: y is 150 or more and less than 200 C: y is 200 or more.

[0234] (10) Film Thickness Change Due to Heat Treatment The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were spin-coated onto an 8-inch silicon wafer using an ACT-8 coater / developer (Tokyo Electron Limited), and heated at 100°C for 2 minutes to produce a 4.0 μm-thick photosensitive resin film. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. The resin-coated wafer was heat-treated at 250°C for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less) using a clean oven (CLH-21CD-S, Koyo Thermo Systems Co., Ltd.), and the film thickness R (μm) was measured. The value of R / 4×100 was taken as the film thickness retention rate after heat treatment.

[0235] The film thickness was judged as follows, and A and B, which indicate a film thickness retention rate of 70% or more, were judged to be acceptable: A: Film thickness retention rate of 75% or more B: Film thickness retention rate of 70% or more but less than 75% C: Film thickness retention rate of less than 70%.

[0236] Synthesis Example 1 Preparation of MPA-2 When 1 kg of commercially available MPA (MPA-1) was used to evaluate the content of the compound represented by general formula (5), it was found to contain 2,000 ppm of DPA. MPA-1 was then continuously contacted with 100 ml of an ion exchange resin (trade name "Amberlyst 16WET", manufactured by Organo Corporation (Rohm & Haas)) packed in an ion exchange resin column, and purified until the DPA content reached 800 ppm, to obtain a purified solvent (MPA-2).

[0237] Synthesis Example 2 Preparation of MPA-3 0.4010 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-3) with a DPA content of 2,400 ppm.

[0238] Synthesis Example 3 Preparation of MPA-4 4.024 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-4) with a DPA content of 6000 ppm.

[0239] Synthesis Example 4 Preparation of MPA-5 6.048 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-5) with a DPA content of 8000 ppm.

[0240] Synthesis Example 5 Preparation of MPA-6 17.02 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-6) with a DPA content of 18,700 ppm.

[0241] Synthesis Example 6 Preparation of MPA-7 19.41 g of DPA was added to 1 kg of commercially available MPA (MPA-1) to obtain MPA (MPA-7) with a DPA content of 21,000 ppm.

[0242] Synthesis Example 7 Synthesis of Polyimide (PI-01) Under a dry nitrogen stream, 32.96 g (90 mmol) of 6FAP as a diamine and 180 g of NMP were weighed and dissolved in a four-neck flask. To this was added 30.03 g (100 mmol) of TDA-100 as an acid dianhydride along with 40.00 g of NMP, and the mixture was stirred at 40°C for 1 hour. Next, 1.863 g (20 mmol) of aniline as a monoamine was added along with 40.00 g of NMP, and the mixture was reacted at 40°C for 1 hour, followed by stirring at 200°C for 4 hours. After stirring, the solution was poured into 2 L of pure water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of polyimide (PI-01). The Mw of the resulting resin was 29,600, and the imidization rate was 100%. The resin powder contained 6.5% by mass of NMP. The evaluation results are shown in Table 1.

[0243] Synthesis Examples 8 to 18, 23 to 28 Synthesis of polyimides (PI-02 to 12, 17 to 22) Synthesis was performed in the same manner as in Synthesis Example 7, except that the types and amounts of the acid dianhydride, monoamine, and diamine were changed to those shown in Table 1, and the polymerization solvent was changed to the type shown. The evaluation results are shown in Table 1.

[0244] Synthesis Example 19: Synthesis of polyimide (PI-13) A powder of polyimide (PI-13) was obtained in the same manner as in Synthesis Example 1, except that the white precipitate was collected by filtration and washed 10 times with pure water. The evaluation results are shown in Table 1.

[0245] Synthesis Example 20: Synthesis of polyimide (PI-14) A polyimide (PI-14) powder was obtained in the same manner as in Synthesis Example 1, except that the white precipitate was collected by filtration and washed 15 times with pure water. The evaluation results are shown in Table 1.

[0246] Synthesis Example 21 Synthesis of polyimide (PI-15) A polyimide (PI-15) powder was obtained in the same manner as in Synthesis Example 1, except that the product was dried in a vacuum dryer at 50° C. for 72 hours and then in a vacuum dryer at 200° C. for 8 hours. The evaluation results are shown in Table 1.

[0247] Synthesis Example 22 Synthesis of Polyimide (PI-16) 30.00 g of PI-01 was weighed out and dissolved in 120 g of ethyl lactate at room temperature. This solution was poured into 1 L of pure water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of polyimide (PI-16). The evaluation results are shown in Table 1.

[0248] Synthesis Example 29: Synthesis of Polyamide (PA-01) Under a dry nitrogen stream, 36.63 g (100 mmol) of 6FAP (diamine) and 7.405 g (50 mmol) of PA were dissolved in 75.00 g of NMP in a four-neck flask and stirred at 80°C for 2 hours. The solution was then cooled to -15°C. After confirming that the solution temperature had reached -15°C, a solution of 22.13 g (75 mmol) of ODBC dissolved in 30 g of NMP was added dropwise, ensuring that the temperature in the reaction system did not exceed 0°C. After the dropwise addition was completed, stirring was continued for 6 hours at 20°C. After the reaction was completed, the solution was poured into 3 L of pure water containing 10 wt% methanol to precipitate a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain polyamide (PA-01). The Mw of the resulting resin was 23,400. The evaluation results are shown in Table 1.

[0249] Synthesis Examples 30 to 37 Synthesis of Polyamides (PA-01 to 09) Synthesis was performed in the same manner as in Synthesis Example 29, except that the types and amounts of the dicarboxylic acid derivative, diamine, and terminal anhydride were changed to those shown in Table 2, and the polymerization solvent was changed to the type shown. The evaluation results are shown in Table 1.

[0250]

[0251]

[0252] Example 1 (A) Polyimide containing a structural unit represented by formula (1) In a dry nitrogen stream, 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 (8.127 × 10) of IPVE was added as a protective agent. －３ mol) was added and stirred at 0° C. for 1 hour. Then, 1.000×10 trifluoroacetic acid (pKa: 0.23) was added as a catalyst. －２ g of 1000 mg ...

[0253] Examples 2 to 40 and Comparative Examples 1 to 4 Synthesis was performed in the same manner as in Example 1, except that the type of base polymer, solvent (type, amount), catalyst (type, pKa, amount), and amount of IPVE were changed as shown in Table 2. The results are shown in Table 2.

[0254]

[0255]

[0256]

[0257] Synthesis Example 38: PI-01-PR40 (40% CP solution) was concentrated using a rotary evaporator, and after the solvent was removed and the solution lost its fluidity, it was removed and the solid concentration was measured. CP and CH were added to this solid so that the solid concentration was 40% and the mass ratio of CP to CH was 5 / 95, to obtain PI-01-PR40CH (40% CH / CP solution).

[0258] Synthesis Example 39: PI-01-PR40 (40% CP solution) was concentrated using a rotary evaporator, and after the solvent was removed and the solution lost fluidity, it was removed and its solid concentration was measured. CP and MIBK were added to this solid so that the solid concentration was 40% and the mass ratio of CP to MIBK was 5 / 95, to obtain PI-01-PR40M (40% MIBK / CP solution).

[0259] Synthesis Example 40: 10.00 g of PI-01-PR40 (40% CP solution) was weighed out, 6.000 g of GBL was added, and solvent substitution was carried out using a rotary evaporator. After solvent substitution, the solid concentration was measured, and GBL was added so that the solid concentration became 40%, thereby obtaining PI-01-PR40G (40% GBL solution).

[0260] Synthesis Example 41: 10.00 g of PI-01-PR40 (40% CP solution) was weighed out, 6.000 g of NMP was added, and solvent substitution was carried out using a rotary evaporator. After solvent substitution, the solid content was measured, and NMP was added so that the solid content concentration became 40%, thereby obtaining PI-01-PR40N (40% NM solution).

[0261] Synthesis Example 42: 10.00 g of PA-01-PR40 (40% CP solution) was weighed out, 6.000 g of GBL was added, and solvent substitution was carried out using a rotary evaporator. After solvent substitution, the solid concentration was measured, and GBL was added so that the solid concentration became 40%, thereby obtaining PA-01-PR40G (40% GBL solution).

[0262] Synthesis Example 43: 10.00 g of PA-01-PR40 (40% CP solution) was weighed out, 6.000 g of NMP was added, and solvent substitution was carried out using a rotary evaporator. After solvent substitution, the solid content concentration was measured, and NMP was added so that the solid content concentration became 40%, thereby obtaining PA-01-PR40N (40% NM solution).

[0263] Example 41 Under yellow light, 2.500 g of a 40% solids CP solution of PI-01-PR10 as component (A), 5.000 × 10 －２ g, 5.000 × 10 lutidine as a heterocyclic amine compound that stabilizes the structure of the constitutional unit represented by formula (1)－３ The resulting photosensitive resin composition had an NMP concentration of 1.00 mass%, a total content of the compounds of general formulas (5) and (6) of 0 mass%, and a concentration of trifluoroacetic acid, an organic acid with a pKa of 0.23, of 10 × 10 －６ The results are shown in Table 3.

[0264] The prepared photosensitive resin composition was subjected to (7) the production of a relief pattern, and the compositions were evaluated for (7-1) the amount of film loss after development, (7-2) sensitivity, (8) storage stability, (9) the effect of leaving the composition after exposure, and (10) the change in film thickness due to heat treatment. The evaluation results are shown in Table 3.

[0265] Examples 42 to 80 and Comparative Examples 5 to 8 Evaluations were carried out in the same manner as in Example 41, except that the composition of each component of the photosensitive resin composition was changed as shown in Table 3. The evaluation results are shown in Table 3.

[0266]

[0267]

[0268]

Claims

1. (A) One or more resins selected from the group consisting of polyimides, polybenzoxazoles, polyamides and copolymers thereof, which include a constituent unit represented by formula (1), (B) Photoacid generator, and, (C) containing solvent, A photosensitive resin composition comprising (C1) a ketone compound represented by formula (2) and / or (C2) a ketone compound represented by formula (3) as the solvent (C). 【Chemistry 1】 (In formula (1), R １ This represents a 3- to 12-valent organic group having 3 to 30 carbon atoms, R ２ This is a monovalent oxymethyl group with 3 to 20 carbon atoms. m represents an integer from 0 to 4, and n represents an integer from 1 to 4. * indicates a bonding site, and a and b independently represent integers of 1 or 2. 【Chemistry 2】 (In formula (2), R ３ This represents a single bond or a 1-2 valent organic group having 1-12 carbon atoms, R ４ R represents a monovalent organic group having 1 to 5 carbon atoms. p represents an integer of 1 or 2. In formula (3), R ５ (where represents a monovalent organic group with 1 to 12 carbon atoms, q represents an integer from 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) comprises a polyimide containing a structural unit represented by formula (1).

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

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

5. Furthermore, the photosensitive resin composition according to claim 1, 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. 【Transformation 3】 (In formula (4), R ６ R represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. ７ Each of these independently represents a monovalent organic group with 1 to 12 carbon atoms, s represents an integer between 2 and 3, and t represents an integer satisfying 0 ≤ t ≤ (s + 1).

6. Furthermore, the compound comprises the compound represented by formula (5) and / or the compound represented by formula (6), The photosensitive resin composition according to claim 1, wherein, when the total amount of the photosensitive resin composition is 100% by mass, the total content of the compound represented by formula (5) and the compound represented by formula (6) is 0.0001% by mass or more and 0.03% by mass or less. 【Chemistry 4】 (In formula (5), R ８ represents a monovalent organic group having 1 to 6 carbon atoms, and R ９ and R １０ each independently represent 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 of 0 or more.)

7. Furthermore, the photosensitive resin composition according to claim 1, further comprising an organic acid with a pKa of -2 to 1.

8. The photosensitive resin composition according to claim 1, wherein the content of fluorine atoms contained in the total resin is greater than 15% by mass, when the total amount of all resin contained in the photosensitive resin composition is taken as 100% by mass.

9. A photosensitive resin sheet obtained by forming a photosensitive resin composition according to any one of claims 1 to 8 in a sheet shape on a support.

10. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

11. a) A step of applying and drying a photosensitive resin composition according to any one of claims 1 to 8 onto a substrate to form a photosensitive resin film, or a step of using a photosensitive resin sheet according to claim 9 to heat-press a photosensitive resin composition onto a substrate. b) A step of exposing the photosensitive resin film or the thermocompressed photosensitive resin composition to light, c) A step of developing the exposed portion of the exposed photosensitive resin film or the exposed portion of the thermocompressed photosensitive resin composition by dissolving or removing it with an alkaline aqueous solution, and d) A step comprising heat treatment of the developed photosensitive resin film or the developed thermocompressed photosensitive resin composition, A method for manufacturing a cured product.

12. A semiconductor device in which the cured product according to claim 10 is disposed as a surface protective film of a semiconductor element or as 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 so as to partially expose the first electrode, and a second electrode provided opposite the first electrode, A display device comprising the cured product described in claim 10 for the insulating layer.

14. A display device comprising a planarization film provided in such a manner that it covers irregularities on a substrate on which thin-film transistors (TFTs) are formed, wherein the planarization film includes the cured product described in claim 10.

15. A method for producing one or more resins selected from the group consisting of polyimides, polybenzoxazoles, polyamides and copolymers thereof, which include a structural unit represented by formula (1), comprising the step of reacting a hydroxyl group contained in the structure of one or more resins selected from the group consisting of polyimides, polybenzoxazoles, polyamides and copolymers thereof with a protective agent in a ketone compound represented by formula (1) (2) and / or a ketone compound represented by formula (3). 【Transformation 5】 (In formula (1), R １ This represents a 3- to 12-valent organic group having 3 to 30 carbon atoms, R ２ This is a monovalent oxymethyl group with 3 to 20 carbon atoms. m represents an integer from 0 to 4, and n represents an integer from 1 to 4. * indicates a bonding site, and a and b independently represent integers of 1 or 2. 【Transformation 6】 (In formula (2), R ３ This represents a single bond or a 1-2 valent organic group having 1-12 carbon atoms, R ４ R represents a monovalent organic group having 1 to 5 carbon atoms. p represents an integer of 1 or 2. In formula (3), R ５ (where represents a monovalent organic group with 1 to 12 carbon atoms, q represents an integer from 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 an organic acid having a pKa of -2 to 1 is used in the step of reacting with the protective agent.

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