Negative photosensitive resin composition, and methods for producing polyimide and cured relief pattern using the same

Abstract

To provide a negative photosensitive resin composition excellent in storage stability, adhesion to sealing materials, and in-plane uniformity and crack resistance upon multilayer formation, or a method for forming a cured relief pattern using the same.SOLUTION: A negative photosensitive resin composition comprises: (A) a polyimide precursor having a structural unit represented by general formula (1) in the figure; (B) a compound including a urethane bond and / or a urea bond; (C) a photopolymerization initiator; and (D) a polymerizable unsaturated monomer having three or more polymerizable functional groups.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a negative-type photosensitive resin composition, and a method for producing a polyimide and a cured relief pattern using the same. [Background technology]

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant relief pattern film by applying, exposing, developing, and curing the composition to a thermal imidization treatment. Such photosensitive resin compositions have the characteristic of enabling a significant reduction in the process compared to conventional non-photosensitive materials.

[0003] There are various methods for packaging semiconductor devices. For example, one of the semiconductor packaging methods is to cover a semiconductor chip with a sealing material (mold resin) to form an element sealing material, and then to form a rewiring layer that electrically connects to the semiconductor chip. Among the semiconductor packaging methods, a semiconductor packaging method called Fan-Out has become mainstream in recent years.

[0004] In a fan-out type semiconductor package, a chip sealing body larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Furthermore, a redistribution layer is formed that extends to the area of ​​the semiconductor chip and the encapsulant. The redistribution layer is formed with a thin film thickness. Furthermore, since the redistribution layer can be formed up to the area of ​​the encapsulant, the number of external connection terminals can be increased.

[0005] For example, as a fan-out type semiconductor device, the device described in the following Patent Document 1 is known. In addition, as a photosensitive resin composition capable of cyclizing (curing) a polyimide precursor at a low temperature, the means described in Patent Document 2 is known. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2011-129767 A [Patent Document 2] International Publication No. 2019 / 189110 Summary of the Invention [Problem to be solved by the invention]

[0007] However, when the curing temperature (thermal imidization temperature) is lowered, there is a problem that the adhesion between the rewiring layer and the sealing material such as the mold resin is reduced. In addition, since the rewiring layer is composed of two or more layers, there are problems such as the in-plane uniformity being easily lost and the first layer being easily cracked. Furthermore, the photosensitive resin composition containing the thermal base generator described in Patent Document 2 does not sufficiently solve the above problems, and further has problems such as a significant decrease in storage stability.

[0008] The present invention has been devised in view of such conventional circumstances, and has as one object to provide a negative type photosensitive resin composition (hereinafter, also simply referred to as "photosensitive resin composition" in this specification) that has excellent storage stability, good adhesion to an encapsulant such as a molding resin, and good in-plane uniformity and crack resistance when formed into a multilayer. Another object is to provide a method for forming a cured relief pattern using the negative type photosensitive resin composition of the present invention. [Means for solving the problem]

[0009] The present inventors have found that the above-mentioned problems can be solved by combining a specific polyimide precursor, a compound containing a specific bond, a photopolymerization initiator, and a specific polymerizable unsaturated monomer, and have completed the present invention. Examples of embodiments of the present invention are listed below. [1] (A) Formula (1): [ka] In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is represented by the following general formula (2): [ka] (In the formula, L1, L2, and L3 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.) It is a monovalent organic group represented by the following formula: A polyimide precursor having a structural unit represented by the formula: (B) a compound containing at least one bond selected from the group consisting of a urethane bond and a urea bond; (C) a photopolymerization initiator, and (D) Polymerizable unsaturated monomer having three or more polymerizable functional groups A negative type photosensitive resin composition comprising: [2] 2. The negative type photosensitive resin composition according to item 1, wherein the compound (B) is a compound having a urea bond. [3] The compound (B) is represented by the following general formula (3) or (4): [ka] In the formula, R7 and R8 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R9 and R 10 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} [ka] {where, R 11 and R 12 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 13 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} 3. The negative type photosensitive resin composition according to item 1 or 2, wherein the compound is represented by the formula: [4] The negative type photosensitive resin composition according to any one of items 1 to 3, wherein the compound (B) contains at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group. [5] 5. The negative type photosensitive resin composition according to any one of items 1 to 4, wherein the polymerizable functional group of the (D) polymerizable unsaturated monomer is a (meth)acrylic group. [6] 6. The negative type photosensitive resin composition according to any one of items 1 to 5, wherein the functional group equivalent (g / mol) of the (D) polymerizable unsaturated monomer is 50 to 300. [7] Y1 in the general formula (1) of the polyimide precursor (A) is represented by the following general formula (5): [ka] {where, R 14 and R 15 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom.} 7. The negative type photosensitive resin composition according to any one of items 1 to 6, wherein the structure is represented by: [8] 8. The negative type photosensitive resin composition according to any one of items 1 to 7, further comprising (E) a rust inhibitor. [9] 9. The negative type photosensitive resin composition according to item 8, wherein the (E) rust inhibitor contains a nitrogen-containing heterocyclic compound.

[10] 10. The negative type photosensitive resin composition according to item 9, wherein the nitrogen-containing heterocyclic compound is an azole compound.

[11] Item 11. The negative type photosensitive resin composition according to item 10, wherein the nitrogen-containing heterocyclic compound is a purine or a purine derivative.

[12] 12. The negative photosensitive resin composition according to any one of items 1 to 11, further comprising: (F) a silane coupling agent.

[13] X1 in the general formula (1) of the polyimide precursor (A) is represented by the following general formulae (20a), (20b), and (20c): [ka] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and 1 is an integer selected from 0 to 2.} [ka] {In the formula, each R6 is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.} [ka] {In the formula, each R6 is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.} 13. The negative type photosensitive resin composition according to any one of items 1 to 12, wherein the structure includes at least one selected from the group consisting of:

[14] The (A) polyimide precursor; 0.1 to 30 parts by mass of the (B) compound based on 100 parts by mass of the (A) polyimide precursor; 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor; 1 to 50 parts by mass of the (D) polymerizable unsaturated monomer based on 100 parts by mass of the (A) polyimide precursor; 14. The negative type photosensitive resin composition according to any one of items 1 to 13, comprising:

[15] 15. A method for producing a polyimide, comprising a step of converting the (A) polyimide precursor contained in the negative photosensitive resin composition according to any one of items 1 to 14 into a polyimide.

[16] (1) A step of applying the negative type photosensitive resin composition according to any one of items 1 to 14 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat treating the relief pattern to form a hardened relief pattern; 2. A method for producing a cured relief pattern comprising: Effect of the Invention

[0010] According to the present invention, it is possible to provide a negative type photosensitive resin composition that has excellent adhesion to an encapsulant and excellent storage stability, and when formed as a multilayer, has excellent in-plane uniformity and can suppress the occurrence of cracks, etc., and also to provide a method for forming a cured relief pattern using the negative type photosensitive resin composition. Also, according to the present invention, it is possible to provide a negative type photosensitive resin composition that has good adhesion to a mold resin used in a fan-out type semiconductor package. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and can be carried out with various modifications within the scope of the gist. Note that throughout this specification, structures represented by the same symbol in a general formula may be the same or different when multiple structures are present in a molecule.

[0012] <Negative-type photosensitive resin composition> The negative photosensitive resin composition according to the present embodiment includes (A) a polyimide precursor, (B) a compound containing at least one selected from the group consisting of a urethane bond and a urea bond, (C) a photopolymerization initiator, and (D) a polymerizable unsaturated monomer having three or more polymerizable functional groups. In this specification, the term "negative" refers to a photosensitive resin composition in which the unexposed area dissolves and the exposed area remains during development.

[0013] From the viewpoint of obtaining high chemical resistance, the negative photosensitive resin composition preferably contains (A) a polyimide precursor, 0.1 to 30 parts by mass of (B) a compound based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of (C) a photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, and 1 to 50 parts by mass of (D) a polymerizable unsaturated monomer having three or more polymerizable functional groups based on 100 parts by mass of the (A) polyimide precursor. This makes it easier to achieve the effects of the present invention.

[0014] (A) Polyimide precursor The polyimide precursor (A) in this embodiment is a resin component contained in a negative photosensitive resin composition, and is converted to a polyimide by a thermal cyclization treatment. The polyimide precursor is a polyamide having a structural unit represented by the following general formula (1). [ka] In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is represented by the following general formula (2): [ka] (In the formula, L1, L2, and L3 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.) It is a monovalent organic group represented by the following formula:

[0015] In the general formula (1), n1 may be an integer of 2 to 150, and from the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition, n1 is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70. In the general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group in which -COOR1 group, -COOR2 group, and -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group, from the viewpoint of achieving both heat resistance and photosensitive properties. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as a group having a structure represented by the following general formula (20). [ka] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}

[0016] The structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the above formula (20) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties. As the X1 group, among the structures represented by the above formula (20), structures represented by at least one of the following formulas (20a), (20b), and (20c) are particularly preferred from the viewpoints of chemical resistance, resolution, and suppression of voids after high-temperature storage test. [ka] {In formulae (20a) to (20c), R6 is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, and m is an integer selected from 0 to 3.} R6 in the general formulae (20a) to (20c) may be the same as or different from R6 in the general formula (21) described below.

[0017] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, and examples thereof include a structure represented by the following formula (21). [ka] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.}

[0018] The structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by the above formula (21) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties. As the Y1 group, the structure represented by the following formula (5) is particularly preferred from the viewpoint of chemical resistance, and in-plane uniformity or crack suppression when formed as a multilayer. [ka] {where, R 14 and R 15 are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom.} Among these, from the viewpoint of the glass transition temperature (Tg) or Young's modulus of the cured film, R 14 and R 15 At least one or both of the groups are preferably a methyl group or a trifluoromethyl group.

[0019] In the above general formula (2), L1 is preferably a hydrogen atom or a methyl group, and L2 and L3 are preferably hydrogen atoms from the viewpoint of photosensitive properties. In addition, in the general formula (2), m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

[0020] In one embodiment, the polyimide precursor (A) is represented by the following general formula (8): [ka] {In the formula, R1, R2, and n1 are defined as for the above general formula (1).} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0021] In the general formula (8), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (2). When the (A) polyimide precursor contains a polyimide precursor having a structural unit represented by the general formula (8), the resolution is particularly high.

[0022] In one embodiment, in view of the effect of including the above formula (5), the polyimide precursor (A) is represented by the following general formula (9): [ka] {In the formula, R1, R2, and n1 are defined as for the above general formula (1).} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0023] In general formula (9), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (2).

[0024] In general formulas (8) and (9), R1, R2, and n1 in one formula may be the same as or different from R1, R2, and n1 in the other formula, respectively.

[0025] (A) Method for preparing polyimide precursor (A) The polyimide precursor is obtained by first reacting a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester body), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group Y1.

[0026] (Preparation of Acid / Ester Forms) In the present embodiment, examples of the tetracarboxylic dianhydride containing a tetravalent organic group X1 that is suitably used for preparing the polyimide precursor (A) include the tetracarboxylic dianhydride represented by the above general formula (20), as well as, for example, pyromellitic anhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl methane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. Preferred examples include pyromellitic dianhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), and 3,3',4,4'-biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0027] In the present embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare the polyimide precursor (A) include 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of the hydroxypropyl acrylate include 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0028] The above-mentioned photopolymerizable alcohols having an unsaturated double bond may be partially mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0029] In addition, a non-photosensitive polyimide precursor prepared only from the alcohols not having an unsaturated double bond may be used as the polyimide precursor by mixing it with the photosensitive polyimide precursor. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0030] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are stirred, dissolved, and mixed in a solvent as described below at a temperature of 20 to 50° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester can be obtained.

[0031] (Preparation of polyimide precursor) The acid / ester (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc., under ice cooling to convert the acid / ester into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 preferably used in this embodiment, dissolved or dispersed in a separate solvent, is added dropwise to the acid / ester to carry out amide polycondensation to obtain the desired polyimide precursor. Alternatively, the acid moiety of the acid / ester is converted into an acid chloride using thionyl chloride or the like, and then the acid is reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0032] Diamines containing a divalent organic group Y1 that are preferably used in this embodiment include diamines having a structure represented by the above general formula (21), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (4,4'-oxydianiline (ODA)), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3 ... ,4'-Diaminodiphenyl sulfone, 3,3'-Diaminodiphenyl sulfone, 4,4'-Diaminobiphenyl, 3,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 4,4'-Diaminobenzophenone, 3,4'-Diaminobenzophenone, 3,3'-Diaminobenzophenone, 4,4'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 1,4-Bis(4-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, 1,3-Bis(3-aminophenoxy) benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl) Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,Examples of the diaminobiphenyl include 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethylbiphenyl-4,4'-diamine (m-TB)), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)-biphenyl, and mixtures thereof.

[0033] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation operations, and then vacuum drying is performed to isolate the desired polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0034] The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0035] (B) Compounds having a urethane bond or a urea bond The (B) compound used in this embodiment contains at least one selected from the group consisting of a urethane bond and a urea bond in its molecular structure (hereinafter, in this embodiment, it is also referred to as a "urethane / urea compound.") Among these (B) compounds, compounds having a urea bond are preferred from the viewpoint of suppressing Cu surface voids or chemical resistance.

[0036] Among the compounds having a urea bond, from the viewpoint of developability, a compound having a structure represented by the following general formula (3) or (4) is more preferable. [ka] In the formula, R7 and R8 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R9 and R 10 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} [ka] {where, R 11 and R 12 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 13 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.}

[0037] Examples of the heteroatom according to the present embodiment include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. In formula (3), R7 and R8 may be a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and preferably contain an oxygen atom from the viewpoint of developability. The carbon number of R7 and R8 may be 1 to 20, and preferably 1 to 10 carbon atoms from the viewpoint of heat resistance, and more preferably 3 to 10 carbon atoms.

[0038] In formula (3), R9 and R 10 R and R may be a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and preferably contain a hydrogen atom or an oxygen atom from the viewpoint of developability. 10The number of carbon atoms may be from 1 to 20, and from the viewpoint of heat resistance, the number of carbon atoms is preferably from 1 to 10, and more preferably from 3 to 10.

[0039] In formula (4), R 11 and R 12 R may each independently be a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and more preferably contains an oxygen atom from the viewpoint of developability. 11 and R 12 The carbon number of R may be 1 to 20, and from the viewpoint of heat resistance, the carbon number is preferably 1 to 10, and more preferably 3 to 10. 13 R may be a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and from the viewpoint of suppressing the occurrence of cracks, it is more preferable that R contains at least one oxygen atom. 13 The carbon number of may be 1 to 20, preferably 2 or more from the viewpoint of containing a heteroatom, and preferably 1 to 18 from the viewpoint of heat resistance.

[0040] In this embodiment, the compound (B) preferably further has at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group, and more preferably has a (meth)acrylic group.

[0041] The reason why the photosensitive resin composition according to the present embodiment contains the compound (B) and thus has good adhesion to the mold resin or good in-plane uniformity when formed as a multilayer is not clear, but the present inventors believe as follows. That is, in one aspect, when the negative photosensitive resin composition is heat-cured at a low temperature of 180° C. or less, the conversion of the polyimide precursor to polyimide tends to be insufficient. In particular, when the negative photosensitive resin composition contains the polymerizable unsaturated monomer (D) having three or more polymerizable functional groups contained in the present embodiment, this tendency becomes more pronounced. On the other hand, the negative photosensitive resin composition according to the present embodiment contains the urethane / urea compound (B), and it is believed that a part of the compound (B) is thermally decomposed to generate amines, etc., which promote the conversion of the polyimide precursor to polyimide. In addition, in a preferred aspect, it is believed that the compound (B) further has a (meth)acrylic group, and when the negative photosensitive resin composition is formed, the compound (B) reacts with the side chain portion of the polyimide precursor by light irradiation and crosslinks, making it easier to exist in the vicinity of the polyimide precursor, and the conversion efficiency can be dramatically improved. Therefore, in the production of the polyimide or the production of the cured relief pattern according to this embodiment, despite the fact that heat curing is performed at a low temperature, the conversion to polyimide is almost complete and the cyclization reaction does not proceed any further. As a result, no shrinkage stress is generated and high adhesion can be maintained. In addition, since the conversion to polyimide is almost complete, when a photosensitive resin composition is coated and prebaked to form a second layer on the first polyimide film, the first layer has sufficient solvent resistance, and therefore it is believed that sufficient in-plane uniformity is achieved.

[0042] In this embodiment, when the (B) compound further has a (meth)acrylic group, the (meth)acrylic equivalent of the (B) compound is preferably 150 to 400 g / mol. When the (meth)acrylic equivalent of the (B) compound is 150 g / mol or more, the chemical resistance of the negative photosensitive resin composition tends to be good, and when it is 400 g / mol or less, the developability tends to be good. The lower limit of the (meth)acrylic equivalent of the (B) compound is more preferably 200 g / mol or more, 210 g / mol or more, 220 g / mol or more, or 230 g / mol or more, more preferably 240 g / mol or more, or 250 g / mol or more, and the lower limit is more preferably 350 g / mol or less, or 330 g / mol or less, and more preferably 300 g / mol or less. The (meth)acrylic equivalent of the (B) compound is even more preferably 210 to 400 g / mol, particularly preferably 220 to 400 g / mol.

[0043] The urethane / urea compound (B) used in this embodiment is preferably a (meth)acrylic group-containing urethane / urea compound having a structure represented by the following general formula (b3). [ka] {In the formula, R3 is a hydrogen atom or a methyl group, A is a group selected from the group consisting of -O-, -NH-, and -NL4-, L4 is a monovalent organic group having 1 to 12 carbon atoms, Z1 is an m2-valent organic group having 2 to 24 carbon atoms, Z2 is a divalent organic group having 2 to 8 carbon atoms, and m2 is an integer of 1 to 3.}

[0044] In formula (b3), R3 may be a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of developability. Z1 may be an m2-valent organic group having 2 to 24 carbon atoms, and the number of carbon atoms is preferably 2 to 20. Here, Z1 may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. If Z1 has 2 or more carbon atoms, the negative photosensitive resin composition tends to have good chemical resistance, and if it has 20 or less carbon atoms, the developability tends to be good. The number of carbon atoms in Z1 is more preferably 3 or more, more preferably 4 or more, and more preferably 18 or less, and even more preferably 16 or less. Z2 may be a divalent organic group having 2 to 8 carbon atoms. Here, Z2 may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. If Z2 has 2 or more carbon atoms, the negative photosensitive resin composition tends to have good chemical resistance, and if it has 8 or less carbon atoms, the heat resistance tends to be good. The number of carbon atoms in Z2 is preferably 6 or less, and more preferably 4 or less. A is a group selected from the group consisting of -O-, -NH-, and -NL4- {wherein L4 is a monovalent organic group having 1 to 12 carbon atoms.}. From the viewpoint of chemical resistance, A is preferably -NH- or -NL4-.

[0045] The (meth)acrylic group-containing urea / urethane compound of the above general formula (b3) can be produced, for example, by reacting an isocyanate compound represented by the following general formula with an amine and / or a hydroxyl group-containing compound. [ka]

[0046] Among the compounds (B) described above, at least one compound selected from the group consisting of the following formulae (b4) to (b7) and (b11) to (b16) is particularly preferred from the viewpoints of chemical resistance, void suppression, and developability. The compounds represented by the following formulae (b4) to (b7) and (b11) to (b16) are also one embodiment of the present invention. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0047] In another embodiment, tetramethylurea can be used as the compound having a urea bond (B).

[0048] In the present embodiment, the (B) compound may be used alone or in combination of two or more. The blending amount of the (B) compound is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The blending amount of the (B) is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and is 30 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0049] (C) Photopolymerization initiator The photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include benzophenone derivatives such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(o- methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferable, particularly from the viewpoint of photosensitivity.

[0050] The amount of the photopolymerization initiator (C) is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the polyimide precursor (A). The amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and 20 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0051] (D) Polymerizable unsaturated monomer having three or more polymerizable functional groups In this embodiment, the photosensitive resin composition contains a polymerizable unsaturated monomer having three or more polymerizable functional groups in its molecular structure as component (D). By containing the polymerizable unsaturated monomer (D), the photosensitive resin composition can have good storage stability and chemical resistance.

[0052] The term "polymerizable functional group" as used herein refers to a functional group capable of forming a bond with another functional group. In the above (D) polymerizable unsaturated monomer, the three or more polymerizable functional groups are preferably at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group. This makes it easier to obtain the effects of the present invention.

[0053] In this embodiment, the polymerizable functional group is preferably a (meth)acrylic group from the viewpoint of developability.

[0054] Examples of such (D) polymerizable unsaturated monomers include trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexaacrylate.

[0055] In the (D) polymerizable unsaturated monomer, one of the three or more polymerizable functional groups may be a (meth)acrylic group, two of them may be (meth)acrylic groups, three or more of them may be (meth)acrylic groups, and when the monomer contains four or more polymerizable functional groups, all of the four polymerizable functional groups may be (meth)acrylic groups. When the three or more polymerizable functional groups contain multiple (meth)acrylic groups, the multiple (meth)acrylic groups may be different from each other or may be the same.

[0056] The polymerizable unsaturated monomer (D) having three or more polymerizable functional groups according to this embodiment preferably has a functional group equivalent (g / mol) of 50 to 300. In addition, when the polymerizable unsaturated monomer (D) contains a (meth)acrylic group, the (meth)acrylic equivalent is preferably 50 to 300, and more preferably 70 to 250. This makes it easier to obtain the effects of the present invention. The functional group equivalent (g / mol) according to this embodiment is a value obtained by dividing the molecular weight by the number of functional groups.

[0057] The polymerizable unsaturated monomer (D) used in the present embodiment may be one type or two or more types.

[0058] The blending amount of the polymerizable unsaturated monomer having three or more polymerizable functional groups (D) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 45 parts by mass or less, based on 100 parts by mass of the polyimide precursor (A). From the viewpoint of polymerizability, the blending amount is more preferably 5 parts by mass or more, and from the viewpoint of physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition, more preferably 40 parts by mass or less.

[0059] solvent The solvent according to the present embodiment may be any solvent capable of uniformly dissolving or suspending the above (A) polyimide precursor, (B) compound having a urethane bond or a urea bond, (C) photopolymerization initiator, and (D) polymerizable unsaturated monomer having three or more polymerizable functional groups. Examples of such solvents include amides, sulfoxides, ureas (excluding the above (B) compound having a urea bond), ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. More specifically, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like can be used.

[0060] In the negative type photosensitive resin composition of the present embodiment, the amount of the solvent used is preferably 10 to 1,000 parts by mass, more preferably 100 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, relative to 100 parts by mass of the polyimide precursor (A).

[0061] (E) Rust inhibitor The negative photosensitive resin composition of the present embodiment may further include a rust inhibitor. The rust inhibitor may be any compound capable of preventing metal from rusting, and may be a nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing heterocyclic compound include an azole compound, a purine, or a purine derivative.

[0062] Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. triazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0063] Particularly preferred examples of the azole compound include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0064] The (E) rust inhibitor may contain purine or a derivative thereof. Examples of the purine derivative contained in the (E) rust inhibitor include adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, 9-methyladenine, 2-hydroxy ...8-aminopurine, 9-methyladenine, 1-methyladenine, 9-methyladenine, 1-methyladenine, 9-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1-methyladenine, 1 -aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, and 8-azahypoxanthine, as well as derivatives thereof.

[0065] When the negative photosensitive resin composition contains an azole compound, or a purine or purine derivative, the amount is preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.1 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A) is 0.05 parts by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative photosensitive resin composition of this embodiment is formed on copper or a copper alloy, while when the amount of the azole compound is 5 parts by mass or less, the photosensitivity is excellent.

[0066] When the negative-type photosensitive resin composition of this embodiment contains an anticorrosive agent (E), the formation of voids in the Cu layer is particularly suppressed. Although the reason for this effect is unclear, it is believed that the anticorrosive agent present on the Cu surface interacts with the (meth)acrylic group, hydroxyl group, alkoxy group, or amino group contained in the preferred embodiment of the urethane / urea compound to form a dense layer near the Cu interface.

[0067] (F) Silane coupling agent The negative photosensitive resin composition of the present embodiment may further contain a silane coupling agent. Examples of the silane coupling agent include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]propionate ... Examples of silane coupling agents include silane coupling agents such as [N-[3-triethoxysilyl]propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propyl succinic anhydride.

[0068] More specifically, the silane coupling agent may be 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxy Examples of the mercaptoethyl silane include 2-mercaptoethyl ethoxy dimethoxy silane, 2-mercaptoethyl tripropoxy silane, 2-mercaptoethyl tripropoxy silane, 2-mercaptoethyl ethoxy dipropoxy silane, 2-mercaptoethyl dimethoxy propoxy silane, 2-mercaptoethyl methoxy dipropoxy silane, 4-mercaptobutyl trimethoxy silane, 4-mercaptobutyl triethoxy silane, and 4-mercaptobutyl tripropoxy silane.

[0069] More specifically, the silane coupling agent may be N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Examples of the silyl silane include urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2).

[0070] More specifically, examples of the silane coupling agent include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methacryloylsilane), ... (triethoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[ 3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyln-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol,Examples of the silane coupling agents include methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. The silane coupling agents listed above may be used alone or in combination.

[0071] Among the above-mentioned silane coupling agents, from the viewpoint of storage stability, preferred are phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and compounds represented by the following formula: [ka] A silane coupling agent having a structure represented by the following formula is preferred.

[0072] When a silane coupling agent is used, the amount of the silane coupling agent is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A). When the negative photosensitive resin composition of this embodiment contains a silane coupling agent (F), void formation in the Cu layer is particularly suppressed. Although the reason for this effect is unclear, it is believed that the silane coupling agent unevenly distributed on the Cu surface interacts with the (meth)acrylic group, hydroxyl group, alkoxy group, or amino group contained in the preferred embodiment of the urethane / urea compound to form a dense layer near the Cu interface.

[0073] (G) Other Ingredients The negative type photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (F). Examples of the components other than the above components (A) to (F) include hindered phenol compounds, organotitanium compounds, sensitizers, polymerizable unsaturated monomers other than the above component (D) (e.g., other photopolymerizable unsaturated monomers), and thermal polymerization inhibitors.

[0074] Hindered phenol compounds To inhibit discoloration on copper surfaces, the negative-acting photosensitive resin composition may optionally contain, for example, a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and the like.

[0075] Examples of the hindered phenol compound include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxyphenyl) 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-di 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among the hindered phenol compounds listed above, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0076] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and from the viewpoint of photosensitivity characteristics, more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0077] Organotitanium Compounds The negative photosensitive resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0078] Usable organotitanium compounds include those in which an organic chemical is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown below in I) to VII):

[0079] I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability and a good pattern for the negative photosensitive resin composition. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0080] II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like.

[0081] III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0082] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0083] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.

[0084] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0085] VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate.

[0086] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0087] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the blending amount of the organic titanium compound is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is obtained.

[0088] Sensitizer The negative photosensitive resin composition of the present embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, and the like. p-Dimethylaminobenzylideneindanone, 2-(p-Dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-Dimethylaminophenylvinylene)benzothiazole, 2-(p-Dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetate Examples of the mercaptobenzoyl compounds include 1-phenyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, and 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These may be used alone or in combination of two or more, for example, two to five types.

[0089] When the photosensitive resin composition contains a sensitizer, the amount of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0090] Other photopolymerizable unsaturated monomers Other photopolymerizable unsaturated monomers according to this embodiment may include unsaturated monomers having one or two polymerizable functional groups in the molecular structure. Examples of such compounds include mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates of propylene glycol or polypropylene glycol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, and ethylene oxide or propylene oxide adducts of these compounds.

[0091] When the photosensitive resin composition contains other photopolymerizable unsaturated monomers, the amount of the other photopolymerizable unsaturated monomers is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less, per 100 parts by mass of the (A) polyimide precursor. When the photosensitive resin composition contains another photopolymerizable unsaturated monomer, the amount of the other photopolymerizable unsaturated monomer may be greater than, less than, or the same as the amount of the polymerizable unsaturated monomer having three or more polymerizable functional groups (D) described above.

[0092] Thermal Polymerization Inhibitor The negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition during storage, particularly in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0093] <Method for Producing Cured Relief Pattern and Semiconductor Device> The method for producing the cured relief pattern of the present embodiment includes the following steps: (1) applying the negative type photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern.

[0094] (1) Photosensitive resin layer formation process In this step, the negative photosensitive resin composition of the present embodiment is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., and a method of spray application with a spray coater, etc., can be used.

[0095] If necessary, the coating film containing the photosensitive resin composition can be dried. As a drying method, air drying, heat drying using an oven or a hot plate, vacuum drying, etc. can be used. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

[0096] (2) Exposure process In this step, the photosensitive resin layer formed above is exposed to an ultraviolet light source or the like. For the exposure method, an exposure device such as a contact aligner, a mirror projection, or a stepper can be used. The exposure can be performed directly or through a photomask or reticle having a pattern.

[0097] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of improving photosensitivity, etc. As for the range of baking conditions, the temperature is preferably 40° C. to 120° C., and the time is preferably 10 seconds to 240 seconds.

[0098] (3) Relief pattern formation process In this process, the unexposed portion of the exposed photosensitive resin layer is developed and removed from the substrate, leaving a relief pattern on the substrate. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

[0099] The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone are preferred. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are used in combination, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Also, two or more types of each solvent, for example, several types, can be used in combination.

[0100] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the above development is heated to dissolve the photosensitive component and imidize the polyimide precursor (A), thereby converting it into a cured relief pattern made of polyimide. As a method of heat curing, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-elevating oven that can set a temperature program. Heating can be performed, for example, at 170°C to 400°C, preferably 170°C to 300°C, more preferably 170°C to 250°C, and even more preferably 170°C to 200°C, for example, for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, and inert gases such as nitrogen and argon can also be used.

[0101] <Polyimide> The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (10). [ka] {In general formula (10), X 1 and Y 1are the same as X1 and Y1 in general formula (1), and m is a positive integer.

[0102] For the same reason, the preferred X1 and Y1 in general formula (1) are also preferred in the polyimide of general formula (10). The number m of repeating units in general formula (10) may be an integer of 2 to 150. In addition, a method for producing a polyimide, which includes a step of converting the polyimide precursor (A) contained in the negative photosensitive resin composition described above into a polyimide, is also one aspect of the present invention.

[0103] <Semiconductor device> In this embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Thus, a semiconductor device can be provided having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for producing a cured relief pattern. This embodiment can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of the process. The semiconductor device of this embodiment can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

[0104] <Display device> In this embodiment, a display device is provided that includes a display element and a cured film provided on the upper portion of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. For example, the cured film may be a surface protective film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for a cathode of an organic EL element.

[0105] The negative photosensitive resin composition of the present embodiment is useful not only for application to the semiconductor device described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. EXAMPLES

[0106] The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polymer or the negative photosensitive resin composition were measured and evaluated according to the following methods.

[0107] <Measurement and evaluation methods> (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Showa Denko Shodex KD-806M, 2 in series, or Showa Denko Shodex 805M / 806M series Standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105 Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min

[0108] (2) Crack evaluation when polyimide film is formed as two layers A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with 200 nm of Ti and 400 nm of Cu in that order using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Next, a negative-type photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film with a thickness of approximately 7 μm. Using a test pattern mask, this coating film was then sprayed with 100 to 500 mJ / cm using Prisma GHI (manufactured by Ultratech Co., Ltd.). 2 The coating was then spray-developed with a coater developer (D-Spin60A, manufactured by SOKUDO) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer on which the relief pattern was formed on Cu was heat-treated for 2 hours in a nitrogen atmosphere at the curing temperature shown in Table 1 using a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg) to obtain a cured relief pattern made of resin with a thickness of about 4 to 5 μm on Cu. Next, the relief pattern after the heat treatment was coated, exposed, and cured again under the same conditions. The cured polyimide film was rated as × (bad) if 4 or more cracks occurred per wafer, △ (acceptable) if 1 to 3 cracks occurred per wafer, and ◯ (good) if no cracks occurred.

[0109] (3) Adhesion test with sealing material As an epoxy-based encapsulant, the R4000 series manufactured by Nagase Chemtex Corporation was prepared. The encapsulant was spin-coated onto an aluminum-sputtered silicon wafer to a thickness of approximately 150 μm, and then thermally cured at 130° C. to harden the epoxy-based encapsulant. The photosensitive resin composition prepared in each Example and Comparative Example was applied onto the above-mentioned epoxy-based cured film to a final film thickness of 10 μm. The applied photosensitive resin composition was exposed to light at a dose of 600 mJ / cm using an aligner (PLA-501F, manufactured by Canon Inc.).2 The entire surface was exposed to ghi rays. Thereafter, the exposed photosensitive resin composition was thermally cured at 180° C. for 2 hours to prepare a first cured film having a thickness of 10 μm.

[0110] The photosensitive resin composition used in forming the first cured film was applied onto the first cured film, and the entire surface was exposed to light under the same conditions as when the first cured film was prepared, and then the film was thermally cured to prepare a second cured film having a thickness of 10 μm. A pin was placed on the sample prepared in the encapsulant deterioration test, and an adhesion test was performed using a pull tester (Quad Group, Sebastian 5 type). That is, the adhesive strength between the epoxy encapsulant and the cured relief pattern prepared from the photosensitive resin composition prepared in each Example and Comparative Example was measured and evaluated according to the following criteria. Evaluation: Adhesive strength 70MPa or more...Adhesion A Adhesive strength: 50MPa or more - less than 70MPa...Adhesion strength B Adhesive strength: 30MPa or more - less than 50MPa...Adhesion strength C Adhesive strength: less than 30MPa Adhesion strength: D

[0111] (4) Storage stability test The viscosity of each of the photosensitive resin compositions prepared in the following examples was measured immediately after preparation and after standing at 23° C. for one month, and the rate of change was calculated. Change rate (%) = Viscosity after leaving at 23℃ for 1 month × 100 / Immediately after mixing The viscosity was measured by the following method. The viscosity of the photosensitive resin composition was measured using an E-type viscometer (RE-80H, manufactured by Toki Sangyo Co., Ltd.) under the conditions of a measurement temperature of 23° C., a rotation speed of 1 to 10 rpm, and a measurement time of 5 minutes. JS2000 (manufactured by Nippon Grease Co., Ltd.) was used as the standard liquid for calibrating the viscometer. The rate of change was evaluated as A if it was 10% or less, B if it was more than 10% and less than 20%, and C if it was more than 20%.

[0112] Production Example 1: (A) Synthesis of Polymer A-1 as a Polyimide Precursor 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2L separable flask, 131.2g of 2-hydroxyethyl methacrylate (HEMA) and 400mL of γ-butyrolactone were added and stirred at room temperature, and 81.5g of pyridine was added while stirring to obtain a reaction mixture. After the end of the heat generation due to the reaction, the reaction mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution obtained by dissolving 206.3g of dicyclohexylcarbodiimide (DCC) in 180mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by the addition of 93.0g of 4,4'-oxydianiline (ODA) suspended in 350mL of γ-butyrolactone over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30mL of ethyl alcohol was added and stirred for 1 hour, and then 400mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The reaction solution obtained was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer formed was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution obtained was dropped into 28 L of water to precipitate the polymer, and the precipitate obtained was filtered off and then vacuum dried to obtain a powdered polymer (polymer A-1). The molecular weight of polymer (A-1) was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

[0113] Production Example 2: (A) Synthesis of Polymer A-2 as a Polyimide Precursor Polymer (A-2) was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of polymer (A-2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0114] Production Example 3: Production method of MOI-D (Compound B-1) 55.1g (0.25mol) of diethylene glycol bis(3-aminopropyl) ether was placed in a 500mL separable flask, and 150mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 77.6g (0.50mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) and 150mL of tetrahydrofuran was added dropwise to the flask over 30 minutes and stirred at room temperature for 5 hours. Then, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-1.

[0115] Production Example 4: Production method of MOI-AEE (Compound B-7) In the above Production Example 4, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of 2-(2-aminoethoxy)ethanol, and 77.6 g of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol), but the synthesis was carried out in the same manner as in Example 1 to obtain compound B-7.

[0116] Production Example 5: Production method of MOI-DOA (Compound B-8) In the above Production Example 4, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 77.6 g of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol), but the synthesis was carried out in the same manner as in Example 1, to obtain compound B-8.

[0117] Production Example 6: (Compound B-11) 2.10g (0.020mol) of diethanolamine was put into a 100mL three-neck flask, 5.6g of tetrahydrofuran was put in, and the mixture was stirred at room temperature. Next, under ice cooling, a solution of 2.67g (0.021mol) of hexyl isocyanate and 5.6g of tetrahydrofuran was added dropwise to the flask over 15 minutes, and the mixture was stirred at room temperature for 4 hours. Then, tetrahydrofuran was distilled off using a rotary evaporator, and compound B-11 was obtained.

[0118] Raw material example: (Compound B-12) A compound similar to Compound B-12 described below was prepared.

[0119] <Example 1> A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B) 8 g of compound B-1 of Example 1 as a compound, (C) 3 g of ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, corresponding to photopolymerization initiator C-1) as a photopolymerization initiator, and (D) 8 g of D-1 compound as a polymerizable unsaturated monomer having three or more polymerizable functional groups were dissolved in a mixture of 120 g of γ-butyrolactone and 30 g of dimethyl sulfoxide. The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of γ-butyrolactone to obtain a negative photosensitive resin composition. The composition was evaluated according to the above-mentioned method. The results are shown in Table 1.

[0120] <Examples 2 to 7, Comparative Example 1> Negative photosensitive resin compositions were prepared in the same manner as in Example 1, except that they were prepared in the blending ratios shown in Table 1, and were evaluated according to the above-mentioned methods. The results are shown in Table 1.

[0121] The compounds (B-1, 7, 8, 11, and 12), the photopolymerization initiator (C-1), and the polymerizable unsaturated monomers having three or more polymerizable functional groups (D-1 to D-2) shown in Table 1 are the following compounds, respectively. [ka] [ka] [ka] [ka] [ka]

[0122] C-1: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (trade name: IRGACURE OXE-02 (OXE-02)) D-1: Pentaerythritol tetraacrylate (Kyoeisha Chemical Co., Ltd., acrylic equivalent: 88 g / mol) D-2: Trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd., acrylic equivalent: 99 g / mol)

[0123] [Table 1] [Industrial Applicability]

[0124] The negative photosensitive resin composition according to the present invention has good storage stability, good adhesion to an encapsulant, and when formed as a multilayer, has excellent in-plane uniformity and excellent crack resistance. The present invention can be suitably used in the field of photosensitive materials useful for manufacturing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) a compound represented by the following general formula (1): 【Chemistry 1】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150; R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of the following general formula (2): 【Chemistry 2】 (In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. It is a monovalent organic group represented by the following formula: A polyimide precursor having a structural unit represented by the formula: (B) a compound having a urea bond, (C) a photopolymerization initiator, and (D) Polymerizable unsaturated monomer having three or more polymerizable functional groups A negative type photosensitive resin composition comprising: The compound (B) is represented by the following general formula (3) or (4): 【Chemistry 3】 {In the formula, R ７ and R ８ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom or a nitrogen atom (excluding functional groups having a charge), and R ９ and R １０ are each independently a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom or a nitrogen atom (excluding functional groups having an electric charge). 【Chemistry 4】 {In the formula, R １１ and R １２ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom or a nitrogen atom (excluding functional groups having a charge), and R １３ is a divalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom or a nitrogen atom (excluding functional groups having a charge). A negative type photosensitive resin composition, which is a compound represented by the formula:

2. 2. The negative type photosensitive resin composition according to claim 1, wherein the polymerizable functional group of the polymerizable unsaturated monomer (D) is a (meth)acrylic group.

3. 3. The negative type photosensitive resin composition according to claim 1, wherein the functional group equivalent (g / mol) of the polymerizable unsaturated monomer (D) is 50 to 300.

4. Y in the general formula (1) of the polyimide precursor (A) １ is represented by the following general formula (5): 【Chemistry 5】 {In the formula, R １４ and R １５ are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom. The negative type photosensitive resin composition according to any one of claims 1 to 3, which has a structure represented by:

5. The negative type photosensitive resin composition according to any one of claims 1 to 4, further comprising (E) a rust inhibitor.

6. The negative type photosensitive resin composition according to claim 5 , wherein the (E) rust inhibitor comprises a nitrogen-containing heterocyclic compound.

7. The negative type photosensitive resin composition according to claim 6 , wherein the nitrogen-containing heterocyclic compound is an azole compound.

8. The negative type photosensitive resin composition according to claim 7 , wherein the nitrogen-containing heterocyclic compound is a purine or a purine derivative.

9. The negative type photosensitive resin composition according to any one of claims 1 to 8, further comprising (F) a silane coupling agent.

10. X in the general formula (1) of the polyimide precursor (A) １ are represented by the following general formulas (20a), (20b), and (20c): 【Chemistry 6】 {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and l is an integer selected from 0 to 2.} 【Chemistry 7】 {In the formula, each R6 is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.} 【Chemistry 8】 {In the formula, each R6 is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.} The negative type photosensitive resin composition according to any one of claims 1 to 9, which has a structure including at least one selected from the group consisting of:

11. The (A) polyimide precursor; 0.1 to 30 parts by mass of the (B) compound based on 100 parts by mass of the (A) polyimide precursor; 0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A); 1 to 50 parts by mass of the polymerizable unsaturated monomer (D) based on 100 parts by mass of the polyimide precursor (A); The negative type photosensitive resin composition according to any one of claims 1 to 10, comprising:

12. A method for producing a polyimide, comprising a step of converting the polyimide precursor (A) contained in the negative photosensitive resin composition according to any one of claims 1 to 11 into a polyimide.

13. (1) applying the negative type photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat treating the relief pattern to form a hardened relief pattern; 2. A method for producing a cured relief pattern comprising:

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