Negative-type photosensitive resin composition, and method for producing polyimide and cured relief pattern using the same.

Abstract

The present invention provides a negative-type photosensitive resin composition that offers high chemical resistance and resolution, and can suppress the generation of voids at the interface between the Cu layer and the resin layer after high-temperature storage testing, as well as a method for forming a cured relief pattern using the same. [Solution] A negative-type photosensitive resin composition is provided, comprising (A) a polyimide precursor represented by the following general formula (1); (B) a compound comprising at least one selected from urethane bonds and urea bonds; and (C) a photopolymerization initiator. In the formula, X1, Y1, n1, R1 and R2 are each defined in this specification. JPEG2026063105000095.jpg54167

Description

[Technical Field]

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

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like have been used as insulating materials for electronic components, and as passivation films, surface protective films, and interlayer insulating films for semiconductor devices, possessing excellent heat resistance, electrical properties, and mechanical properties. Among these resins, those provided in the form of photosensitive resin compositions allow for the easy formation of heat-resistant relief pattern films through thermal imidization treatment by coating, exposure, development, and curing of the composition. Such photosensitive resin compositions have the advantage of significantly shortening the process compared to conventional non-photosensitive materials.

[0003] Incidentally, semiconductor devices (hereinafter also referred to as "devices") are mounted on printed circuit boards in various ways depending on the purpose. Conventionally, devices were generally manufactured using the wire bonding method, in which thin wires are connected from the external terminals (pads) of the device to the lead frame. However, in recent years, as devices have become faster and their operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting have begun to affect the operation of the device. Therefore, in mounting devices for high-end applications, it has become necessary to precisely control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] Therefore, flip-chip mounting has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on it, and then the chip is flipped over and directly mounted on a printed circuit board (see, for example, Patent Document 1). Because the wiring distance can be precisely controlled in this flip-chip mounting, it has been adopted for high-end applications handling high-speed signals, and also for mobile phones and the like due to its small mounting size, and demand is rapidly expanding. When materials such as polyimide, polybenzoxazole, and phenolic resin are used in flip-chip mounting, the process involves forming a metal wiring layer after the pattern of the resin layer has been formed. The metal wiring layer is usually formed by plasma etching the surface of the resin layer to roughen the surface, then sputtering a metal layer with a thickness of 1 μm or less to serve as a seed layer for plating, and then performing electroplating using that metal layer as an electrode. In this case, titanium (Ti) is generally used as the metal for the seed layer, and copper (Cu) is used as the metal for the redistribution layer formed by electroplating.

[0005] For such metal redistribution layers, high adhesion between the redistributed metal layer and the resin layer is required after reliability testing. Examples of reliability tests include: a high-temperature storage test in which the wire is stored in air at a high temperature of 125°C or higher for 100 hours or more; a high-temperature operation test in which the wire is assembled and voltage is applied while the operation is confirmed under storage conditions of 100 hours or more at a temperature of about 125°C in air; a temperature cycle test in which the wire is cycled between a low temperature of about -65°C to -40°C and a high temperature of about 125°C to 150°C in air; a high-temperature and high-humidity storage test in which the wire is stored at a temperature of 85°C or higher in a water vapor atmosphere with a humidity of 85% or higher; a high-temperature and high-humidity bias test, which is the same test as the high-temperature and high-humidity storage test but performed with the wire assembled and voltage applied; and a solder reflow test in which the wire is passed through a solder reflow oven at 260°C multiple times in air or under nitrogen. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2001-338947 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, in conventional reliability tests, particularly high-temperature storage tests, there was a problem where voids would form at the interface between the rewired Cu layer and the resin layer after the test. When voids form at the interface between the Cu layer and the resin layer, the adhesion between the two decreases.

[0008] In addition to the void problem, metal redistribution layers require chemical resistance, and there is also a growing demand for miniaturization. For this reason, photosensitive resin compositions used in the formation of semiconductor redistribution layers, in particular, are required to suppress void formation while exhibiting high chemical resistance and resolution.

[0009] The present invention has been devised in view of the above-mentioned conventional circumstances, and one of its objectives is to provide a negative-type photosensitive resin composition (hereinafter simply referred to as "photosensitive resin composition" in this specification) that can obtain high chemical resistance and resolution, and can suppress the generation of voids at the interface of the Cu layer in contact with the resin layer after high-temperature storage testing. Another objective is to provide a method for forming a cured relief pattern using the negative-type photosensitive resin composition of the present invention.

[0010] In recent years, fan-out type semiconductor packages have attracted attention. In fan-out type semiconductor packages, a chip encapsulation 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. Also, because the redistribution layer can be formed in the area of ​​the encapsulant, the number of external connection terminals can be increased. However, fan-out type semiconductor packages require even lower curing temperatures, which results in reduced adhesion with encapsulants such as molding resins, thus requiring further improvements. [Means for solving the problem]

[0011] The inventors have discovered that the above problems can be solved by combining a polyimide precursor with a specific structure, a (meth)acrylate having a specific structure, and a photopolymerization initiator, and have completed the present invention. Examples of embodiments of the present invention are listed below. [1] (A) A polyimide precursor represented by the following general formula (1); (B) Compounds comprising at least one selected from urethane bonds and urea bonds; and (C) Photopolymerization initiator A negative-type photosensitive resin composition containing [the specified element]. [ka] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer between 2 and 150, and R1 and R2 are independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a monovalent organic group represented by the following general formula (2).} [ka] {In the formula, L1, L2, and L3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.} [2] The negative-type photosensitive resin composition according to item 1, wherein the above-mentioned compound (B) is a compound having a urea bond. [3] The negative-type photosensitive resin composition according to item 1 or 2, wherein the above-mentioned compound (B) further comprises at least one functional group selected from a (meth)acrylic group, a hydroxyl group, an alkoxy group, and an amino group. [4] The negative-type photosensitive resin composition according to any one of items 1 to 3, wherein the compound (B) above is a compound having a (meth)acrylic group and a urea bond, and the (meth)acrylic equivalent is 150 to 400 g / mol. [5] The negative photosensitive resin composition according to any one of Items 1 to 3, wherein the above-mentioned (B) compound is a compound having a (meth)acrylic group and a urea bond, and the (meth)acrylic equivalent is 210 to 400 g / mol. [6] The negative photosensitive resin composition according to any one of Items 1 to 3, wherein the above-mentioned (B) compound is a compound having a (meth)acrylic group and a urea bond, and the (meth)acrylic equivalent is 220 to 400 g / mol. [7] The negative photosensitive resin composition according to any one of Items 1 to 6, wherein the above-mentioned (B) compound has a structure represented by the following general formula (3). [Chemical formula] {In the formula, R3 is a hydrogen atom or a methyl group; A is one 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 a divalent 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.} [8] The negative photosensitive resin composition according to any one of Items 1 to 7, wherein the above-mentioned (B) compound further contains a (meth)acrylic group and at least one functional group selected from a hydroxyl group, an alkoxy group, and an amino group. [9] The negative photosensitive resin composition according to any one of Items 1 to 8, wherein the above-mentioned (B) compound is at least one compound selected from the group consisting of the following formulas (4) to (7) and (11) to (14). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [ka] [ka] [ka]

[10] (D) A negative-type photosensitive resin composition according to any one of items 1 to 9, further comprising a rust inhibitor.

[11] The above (D) rust inhibitor is a negative-type photosensitive resin composition as described in item 10, comprising a nitrogen-containing heterocyclic compound.

[12] The above nitrogen-containing heterocyclic compound is an azole compound, in the negative-type photosensitive resin composition described in item 11.

[13] The above nitrogen-containing heterocyclic compound is a purine derivative, in the negative-type photosensitive resin composition described in item 11.

[14] (E) A negative-type photosensitive resin composition according to any one of items 1 to 13, further comprising a silane coupling agent.

[15] A negative-type photosensitive resin composition according to any one of items 1 to 14, wherein X1 in the polyimide precursor (A) above comprises at least one selected from the group consisting of the following general formulas (20a), (20b), and (20c). [ka] [ka] [ka] {In the formula, R6 are independently a hydrogen atom, a fluorine atom, and C1~C}. 10 hydrocarbon groups, and C1~C 10 It is a monovalent group selected from the group consisting of fluorine-containing hydrocarbon groups, where l is an integer selected from 0 to 2, and m is an integer selected from 0 to 3.

[16] A negative-type photosensitive resin composition according to any one of items 1 to 15, wherein Y1 in the polyimide precursor (A) above comprises at least one selected from the group consisting of the following general formulas (21a), (21b), and (21c). [ka] [ka] [ka] {In the formula, R6 are independently a hydrogen atom, a fluorine atom, and C1~C}. 10 hydrocarbon groups, and C1~C 10 It is a monovalent group selected from the group consisting of fluorine-containing hydrocarbon groups, and n is an integer selected from 0 to 4.

[17] The above (A) polyimide precursor is the following general formula (8): [ka] {In the formula, n1 is an integer between 2 and 150, and R1 and R2 are, independently, a hydrogen atom or a monovalent organic group.} A negative-type photosensitive resin composition according to any one of items 1 to 16, comprising a polyimide precursor having a structural unit represented by .

[18] The above (A) polyimide precursor is the following general formula (9): [ka] {In the formula, n1 is an integer between 2 and 150, and R1 and R2 are, independently, a hydrogen atom or a monovalent organic group.} A negative-type photosensitive resin composition according to any one of items 1 to 17, comprising a polyimide precursor having a structural unit represented by .

[19] The above (A) polyimide precursor is the following general formula (8): [ka] {In the formula, n1 is an integer between 2 and 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group, which may be the same as or different from R1, R2, and n1 in general formula (9).} A structural unit represented by, The following general formula (9): [ka] {In the formula, n1 is an integer between 2 and 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group, which may be the same as or different from R1, R2, and n1 in general formula (8).} It is a copolymer with structural units represented by, or A negative-type photosensitive resin composition according to any one of items 1 to 18, which is a blend of a polyimide precursor having a structural unit represented by the above general formula (8) and a polyimide precursor having a structural unit represented by the above general formula (9).

[20] The negative-type photosensitive resin composition according to item 19, wherein the (A) polyimide precursor is a copolymer of the structural unit represented by the general formula (8) and the structural unit represented by the general formula (9). [twenty one] 100 parts by mass of the above (A) polyimide precursor, Based on 100 parts by mass of the above (A) polyimide precursor, 0.1 to 30 parts by mass of the above (B) compound and Based on 100 parts by mass of the above (A) polyimide precursor, 0.1 to 20 parts by mass of the above (C) photopolymerization initiator and A negative-type photosensitive resin composition according to any one of items 1 to 20, including the following: [twenty two] A method for producing polyimide, comprising the step of converting a negative-type photosensitive resin composition described in any one of items 1 to 21 into a polyimide. [twenty three] (1) A step of applying a negative-type photosensitive resin composition described in any one of items 1 to 21 onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the above photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the above relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element]. [twenty four] A compound represented by the following formula (5). [ka] [twenty five] A compound represented by the following formula (6). [ka]

[26] A compound represented by the following formula (7). [ka]

[27] A compound represented by the following formula (11). [ka]

[28] A compound represented by the following formula (12). [ka]

[29] A compound represented by the following formula (13). [ka]

[30] A compound represented by the following formula (14). [ka] [Effects of the Invention]

[0012] The present invention provides a negative-type photosensitive resin composition that offers high chemical resistance and resolution, suppresses void generation at the interface of the Cu layer to the resin layer after high-temperature storage testing, and provides a method for forming a cured relief pattern using the negative-type photosensitive resin composition. Furthermore, the present invention provides a negative-type photosensitive resin composition that exhibits good adhesion to molding resins used in fan-out type semiconductor packages. [Modes for carrying out the invention]

[0013] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). However, the present invention is not limited to the following embodiments and can be implemented in various modifications within the scope of its gist. Throughout this specification, structures represented by the same reference numerals in a general formula may be identical or different when multiple such structures exist in a molecule.

[0014] <Negative-type photosensitive resin composition> The negative-type photosensitive resin composition according to this embodiment comprises (A) a polyimide precursor; (B) a compound containing at least one selected from urethane bonds and urea bonds; and (C) a photopolymerization initiator.

[0015] From the viewpoint of obtaining high chemical resistance, the negative-type photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B) compound based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

[0016] (A) Polyimide precursor In this embodiment, (A) the polyimide precursor is a resin component contained in a negative-type photosensitive resin composition, and is converted to polyimide by heat cyclization treatment. The polyimide precursor is a polyamide having a structure 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 between 2 and 150, and R1 and R2 are, independently, a hydrogen atom or a monovalent organic group.}

[0017] At least one of R1 and R2 is a monovalent organic group represented by the following general formula (2). [ka] {In the formula, L1, L2, and L3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.}

[0018] In general formula (1), n1 is not limited to an integer between 2 and 150, but from the viewpoint of photosensitive properties and mechanical properties of the negative-type photosensitive resin composition, an integer between 3 and 100 is preferred, and an integer between 5 and 70 is more preferred. In general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, in terms of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group, the -COOR2 group and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group. Specifically, as the tetravalent organic group represented by X1, examples include, but are not limited to, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, a group having the structure represented by the following general formula (20). [ka] {In the formula, R6 represents a hydrogen atom, a fluorine atom, and C1~C}. 10 hydrocarbon groups, and C1~C 10 It is a monovalent group selected from the group consisting of fluorine-containing hydrocarbon groups, where 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.

[0019] 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 preferable in that it achieves both heat resistance and photosensitive characteristics. Among the structures represented by the above formula (20), as the X1 group, the structures represented by the following formulas (20a), (20b), and (20c) are particularly preferable from the viewpoints of chemical resistance, resolution, and void suppression after a high-temperature storage test. [Chemical formula] {In the formula, each R6 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C 10 hydrocarbon group, and a C1-C 10 fluorinated hydrocarbon group, 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.} R6 in the general formulas (20a) to (20c) may be the same as or different from R6 in the general formulas (21a) to (21c) described later.

[0020] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in that it achieves both heat resistance and photosensitive characteristics. For example, the structure represented by the following formula (21) can be mentioned, but it is not limited thereto. [Chemical formula] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C 10 hydrocarbon group, and a C1-C 10 fluorinated hydrocarbon group, and n is an integer selected from 0 to 4.}

[0021] 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 preferable in that it achieves both heat resistance and photosensitive characteristics. Among the structures represented by the above formula (21), as the Y1 group, the structures represented by the following formulas (21a), (21b), and (21c) are particularly preferable from the viewpoints of chemical resistance, resolution, and void suppression after a high-temperature storage test. [ka] {In the formula, R6 are independently a hydrogen atom, a fluorine atom, and C1~C}. 10 hydrocarbon groups, and C1~C 10 R6 in general formulas (21a) to (21c) may be the same as or different from R6 in the aforementioned general formulas (20a) to (20c).

[0022] 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 photosensitivity. Also, m1 is an integer between 2 and 10, preferably between 2 and 4, from the viewpoint of photosensitivity.

[0023] In one embodiment, (A) the polyimide precursor is given by the following general formula (8): [ka] {In the formula, R1, R2, and n1 are as defined above.} It is preferable that the polyimide precursor has a structural unit represented by the above formula (8). In general formula (8), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by the above general formula (2). (A) The resolution effect is particularly enhanced when the polyimide precursor includes a polyimide precursor having a structural unit represented by general formula (8).

[0024] In one embodiment, (A) the polyimide precursor is given by the following general formula (9): [ka] {In the formula, R1, R2, and n1 are as defined above.} It is preferable that the polyimide precursor has a structural unit represented by .

[0025] In general formula (9), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by general formula (2). (A) The resolution effect is further enhanced, in particular, by including a polyimide precursor having a structural unit represented by general formula (9) in addition to a polyimide precursor having a structural unit represented by general formula (8).

[0026] (A) The polyimide precursor is a mixture of a polyimide precursor having a structural unit represented by general formula (8) and a polyimide precursor having a structural unit represented by general formula (9), or a copolymer of the structural unit represented by general formula (8) and the structural unit represented by general formula (9), which is particularly preferable from the viewpoint of chemical resistance, resolution, and suppression of voids after high-temperature storage tests. 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.

[0027] (A) Method for preparing polyimide precursors (A) The polyimide precursor is first obtained by reacting a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 with photopolymerizable alcohols having unsaturated double bonds and optionally alcohols without unsaturated double bonds to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as acid / ester), and then by amide polycondensation of this with diamines containing the aforementioned divalent organic group Y1.

[0028] (Preparation of acid / ester compounds) In this embodiment, suitable tetracarboxylic dianhydrides containing a tetravalent organic group X1 for preparing (A) polyimide precursors include the tetracarboxylic dianhydride shown in the general formula (20) above, as well as, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and the like. Preferably, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride (ODPA), and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) are used, but the product is not limited to these. These can be used individually or in combination of two or more.

[0029] In this embodiment, suitable photopolymerizable alcohols having unsaturated double bonds for preparing (A) polyimide precursors include, for example, 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, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples include hydroxypropyl acrylate, 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.

[0030] In addition to the above-mentioned photopolymerizable alcohols having unsaturated double bonds, it is also possible to use a mixture of some alcohols without unsaturated double bonds, 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.

[0031] Furthermore, as a polyimide precursor, a non-photosensitive polyimide precursor prepared solely from alcohols that do not have the above-mentioned unsaturated double bonds may be used in combination with the photosensitive polyimide precursor. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor be 200 parts by mass or less, based on 100 parts by mass of the photosensitive polyimide precursor.

[0032] By stirring and dissolving the above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohols in a solvent as described later, in the presence of a basic catalyst such as pyridine, at a temperature of 20-50°C for 4-10 hours, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0033] (Preparation of polyimide precursors) To the above acid / ester mixture (typically a solution in a solvent described later), a suitable dehydrating condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, is added and mixed under ice cooling to form a polyacid anhydride from the acid / ester mixture. Then, a diamine containing a divalent organic group Y1, which is preferably used in this embodiment, is dissolved or dispersed separately in a solvent and added dropwise to this mixture to perform amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the above acid / ester mixture can be acid-chlorinated using thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0034] Diamines containing the divalent organic group Y1 that are preferably used in this embodiment include diamines having the structure shown in the general formula (21) above, 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 sulfone, 3 ,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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 C) 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., for example, 3,3'-dimethyl-4Examples include, but are not limited to, 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'-dimethitoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0035] After the amide polycondensation reaction is complete, any water-absorbing by-products of the dehydrating condensation agent present in the reaction solution are filtered off as needed. Then, a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate it. Further purification of the polymer is carried out by repeating the redissolution and reprecipitation operations, and the polymer is then vacuum-dried to isolate the target polyimide precursor. To improve the degree of purification, the solution of this polymer may be passed through a column packed with anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0036] The molecular weight of the polyimide precursor (A) described above is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by weight-average molecular weight in terms of polystyrene equivalent using gel permeation chromatography. When the weight-average molecular weight is 8,000 or higher, the mechanical properties are good, and when it is 150,000 or lower, the dispersibility in the developer is good and the relief pattern resolution is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvents for gel permeation chromatography. The weight-average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko Corporation.

[0037] (B) Compounds having urethane bonds or urea bonds Compound (B) used in this embodiment contains at least one selected from urethane bonds and urea bonds in its molecular structure (hereinafter, in this embodiment, it is also referred to as "urethane / urea compound"). The compound used in this embodiment is not limited to any other structure as long as it has urethane bonds and / or urea bonds in its molecular structure. Among these, it is preferable to have urea bonds from the viewpoint of suppressing Cu surface voids and chemical resistance. In this embodiment, it is preferable that compound (B) further has at least one functional group selected from the group consisting of (meth)acrylic groups, hydroxyl groups, alkoxy groups, and amino groups.

[0038] The reason why the inclusion of compound (B) in this embodiment results in good chemical resistance and resolution is not clear, but the inventors believe the following. In one embodiment, since the negative-type 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. On the other hand, in the negative-type photosensitive resin composition of this embodiment, by containing the urethane / urea compound (B), a portion of compound (B) undergoes thermal decomposition, generating amines, etc., and these amines, etc., are thought to promote the conversion of the polyimide precursor to polyimide. Furthermore, in a preferred embodiment, if compound (B) further has (meth)acrylic groups, especially when used in a negative-type photosensitive resin composition, compound (B) reacts with the side chain portion of the polyimide precursor upon light irradiation, crosslinking and making it easier to exist in the vicinity of the polyimide precursor, thereby dramatically increasing the conversion efficiency.

[0039] In this embodiment, if compound (B) further has (meth)acrylic groups, the (meth)acrylic equivalent of compound (B) is preferably 150 to 400 g / mol. When the (meth)acrylic equivalent of compound (B) is 150 g / mol or more, the chemical resistance of the negative-type 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 compound (B) is more preferably 200 g / mol or more, 210 g / mol or more, 220 g / mol or more, 230 g / mol or more, even more preferably 240 g / mol or more, 250 g / mol or more, and the lower limit is more preferably 350 g / mol or less, 330 g / mol or less, and even more preferably 300 g / mol or less. The (meth)acrylic equivalent of compound (B) is more preferably 210 to 400 g / mol, and particularly preferably 220 to 400 g / mol.

[0040] 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 (3). [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 from 1 to 3.}

[0041] R3 is not limited to a hydrogen atom or a methyl group, but a methyl group is preferred from the viewpoint of developability. Z1 is not limited to an m2 valent organic group having 2 to 20 carbon atoms. Here, Z1 may also include heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. If the number of carbon atoms in Z1 is 2 or more, the negative-type photosensitive resin composition tends to have good chemical resistance, and if the number of carbon atoms is 20 or less, the developability tends to be good. The number of carbon atoms in Z1 is preferably 3 or more, more preferably 4 or more, preferably 18 or less, and more preferably 16 or less. Z2 is not limited to a divalent organic group having 2 to 8 carbon atoms. Here, Z2 may also include heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. If the number of carbon atoms in Z2 is 2 or more, the negative-type photosensitive resin composition tends to have good chemical resistance, and if the number of carbon atoms is 8 or less, 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-. From the viewpoint of chemical resistance, A is preferably -NH- or -NL4-.

[0042] The method for producing the (meth)acrylic group-containing urea / urethane compound of the above general formula (3) is not particularly limited, but can be obtained, for example, by reacting an isocyanate compound represented by the following general formula with an amine and / or hydroxyl group-containing compound. [ka]

[0043] Among the compounds (B) described above, at least one compound selected from the group consisting of the following formulas (4) to (7) and (11) to (14) is particularly preferred from the viewpoint of chemical resistance, void suppression, and developability. The compounds represented by the following formulas (4) to (7) and (11) to (14) are also embodiments of the present invention. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0044] The urethane / urea compound (B) of this embodiment preferably further has at least one functional group selected from the group consisting of hydroxyl groups, alkoxy groups, and amino groups. By containing at least one selected from the group consisting of hydroxyl groups, alkoxy groups, and amino groups, the urethane / urea compound of this embodiment tends to have good adhesion to the molding resin used in a fan-out type semiconductor package, for example, in one embodiment. The reason for this is not clear, but the inventors believe it to be as follows. That is, in one embodiment, the negative-type photosensitive resin composition is heat-cured at a low temperature of 180°C or less. At such low temperatures, the epoxy resin contained in the molding resin used in the fan-out type semiconductor package has an epoxy structure without partial ring opening, and this epoxy structure tends to interact with the hydroxyl groups, alkoxy groups, amino groups, etc. contained in the urethane / urea compound (B). On the other hand, it is presumed that the urethane / urea structure contained in compound (B) interacts with the polyimide resin, resulting in high adhesion to the molding resin. Among these functional groups, hydroxyl groups and alkoxy groups are preferred, and hydroxyl groups are particularly preferred. From the viewpoint of adhesion to the mold resin, chemical resistance, and suppression of Cu voids, it is more preferable that compound (B) has (meth)acrylic groups and hydroxyl groups in its molecular structure in addition to the urethane / urea structure.

[0045] The alkoxy group is more preferably a carbon-1 to carbon-10 alkoxy group such as a methoxy group, ethoxy group, or propoxy group. Examples of such compounds include those having the following structures. [ka] [ka] [ka]

[0046] In this embodiment, compound (B) may be used alone or as a mixture of two or more types. The amount of compound (B) blended is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass, per 100 parts by mass of polyimide precursor (A). The amount of (B) blended is 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and 30 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition.

[0047] (C) Photopolymerization initiator The photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of photoradical polymerization initiators include: benzophenone derivatives such as benzophenone, o-benzoylmethyl 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 benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl Examples of photopolymerization initiators include, but are not limited to, oximes such as 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 particularly preferred in terms of photosensitivity.

[0048] (C) The amount of photopolymerization initiator added is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 1 part by mass to 8 parts by mass, per 100 parts by mass of (A) polyimide precursor. The above amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition.

[0049] (D) Rust inhibitor The negative-type photosensitive resin composition of this embodiment may further contain a rust inhibitor. The rust inhibitor is not limited as long as it can prevent metal corrosion, but examples include nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives.

[0050] Azole compounds 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, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. Examples include azoles, 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-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, and 1-methyl-1H-tetrazol.

[0051] Particularly preferred azole compounds include toltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used individually or in combination of two or more.

[0052] Purine derivatives include purine, 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, and 8-aminoadenin Examples include 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.

[0053] When the negative-type photosensitive resin composition contains an azole compound or a purine derivative, the amount of the compound is preferably 0.05 to 5 parts by mass per 100 parts by mass of (A) polyimide precursor, and more preferably 0.1 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the azole compound per 100 parts by mass of (A) polyimide precursor is 0.05 parts by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative-type 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.

[0054] When the negative-type photosensitive resin composition of this embodiment contains (D) a rust inhibitor, void formation in the Cu layer is particularly suppressed. The reason for this effect is not entirely clear, but it is thought that the rust inhibitor 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, forming a dense layer near the Cu interface.

[0055] (E) Silane coupling agent The negative-type photosensitive resin composition of this embodiment may further contain a silane coupling agent. Examples of silane coupling agents 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, and N-[3-(triethoxysilyl)propyl Examples of silane coupling agents include propyl phthalamide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propylsuccinic anhydride.

[0056] More specifically, as silane coupling agents, there are 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Cyra Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Co., Ltd.: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercapto Toethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name) LS3610, manufactured by Azmax Co., Ltd.: Product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: Product 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)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 Co., Ltd.: product name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: product 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(methoxyethoxysilane), te Trakis(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-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butyl Examples include, but are not limited to, methylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethyl isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. These may be used individually or in combination.

[0057] Among the silane coupling agents listed above, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agents having a structure represented by the following formula are preferred from the viewpoint of storage stability. [ka]

[0058] When using a silane coupling agent, the preferred amount is 0.1 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor. When the negative-type photosensitive resin composition of this embodiment contains (E) a silane coupling agent, void formation in the Cu layer is particularly suppressed. The reason for this effect is not entirely clear, but it is thought that the silane coupling agent, which is unevenly distributed on the Cu surface, interacts with (meth)acrylic groups, hydroxyl groups, alkoxy groups, or amino groups contained in the preferred embodiment of the urethane / urea compound, forming a dense layer near the Cu interface.

[0059] (F) Other ingredients The negative-type photosensitive resin composition of this embodiment may further contain components other than those listed above (A) to (E). Examples of components other than those listed (A) to (E) are, but are not limited to, solvents, hindered phenol compounds, organotitanium compounds, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors.

[0060] solvent Examples of solvents include amides, sulfoxides, ureas, 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, tetramethylurea, 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, etc. can be used. In particular, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred from the viewpoint of resin solubility, stability of the resin composition, and adhesion to the substrate.

[0061] Among such solvents, those that completely dissolve the resulting polymer are particularly preferred, and examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

[0062] In the negative-type photosensitive resin composition of this embodiment, the amount of solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of (A) polyimide precursor.

[0063] Hindered phenol compounds To suppress discoloration on the copper surface, the negative-type photosensitive resin composition may optionally contain 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'-thiobis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylpheno (Iol), 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], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 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, 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-Triadin-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-Triadin-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-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-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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 Examples include, but are not limited to, 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 these, 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.

[0064] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound per 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when it is 20 parts by mass or less, the photosensitivity is excellent.

[0065] Organic titanium compounds The negative-type photosensitive resin composition of this embodiment may contain an organic titanium compound. By including an organic titanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0066] Suitable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: 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 negative-type photosensitive resin compositions. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate). II) Tetraalkoxy titanium 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 tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0067] In particular, the organotitanium 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 achieving better chemical resistance. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are especially preferred.

[0068] When incorporating an organotitanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyimide precursor (A). When the amount of organotitanium 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 achieved.

[0069] Sensitizer The negative-type photosensitive resin composition of this embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include Michla'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, and p-dimethylaminocinnamyridane indano n, p-dimethylaminobenzylidene indanone, 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-acetone Examples include 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, 2-(p-dimethylaminobenzoyl)styrene, etc. These can be used individually or in combination, for example, by using a combination of 2 to 5 types.

[0070] When the photosensitive resin composition contains a sensitizer, the amount added is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0071] Photopolymerizable unsaturated monomers The negative-type photosensitive resin composition may optionally contain monomers having photopolymerizable unsaturated bonds (photopolymerizable unsaturated monomers) to improve the resolution of the relief pattern. Preferred monomers include (meth)acrylic compounds that undergo radical polymerization with a photopolymerization initiator, and are not limited to the following: mono- or diacrylate and methacrylate of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol; mono-, di- or triacrylate and methacrylate of glycerol; cyclohexane diacrylate and dimethacrylate; 1,4-butanediol diacrylate and dimethacrylate; and 1,6-hexane. Examples of compounds include diacrylates and dimethacrylates of diols, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri- or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0072] If the photosensitive resin composition contains a photopolymerizable unsaturated monomer, the amount of monomer added is preferably 1 to 50 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0073] Thermal polymerization inhibitors The negative-type photosensitive resin composition of this embodiment may optionally contain a thermal polymerization inhibitor to improve the viscosity and photosensitivity stability of the negative-type photosensitive resin composition, especially when stored in a solvent-containing solution. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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.

[0074] <Method for manufacturing a hardened relief pattern and semiconductor device> The method for manufacturing the cured relief pattern of this embodiment is: (1) A step of applying the negative-type photosensitive resin composition of this embodiment described above onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the above photosensitive resin layer, (3) A step of developing the above photosensitive resin layer after exposure to form a relief pattern, (4) The process includes the step of heat-treating the relief pattern to form a hardened relief pattern.

[0075] (1) Photosensitive resin layer formation process In this process, the negative-type photosensitive resin composition of this embodiment is applied to a substrate and, if necessary, subsequently dried to form a photosensitive resin layer. Conventional application methods for photosensitive resin compositions can be used, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., and spray application using a spray coater.

[0076] If necessary, the coating containing the photosensitive resin composition can be dried. Drying methods include air drying, heating with an oven or hot plate, and vacuum drying. Specifically, when air drying or heating is performed, drying can be carried out at a temperature of 20°C to 140°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

[0077] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to ultraviolet light or the like. Exposure devices such as contact aligners, mirror projection machines, and steppers can be used. Exposure can be performed via a patterned photomask or reticle, or directly.

[0078] Subsequently, if necessary, post-exposure baking (PEB) and / or pre-development baking may be performed using any combination of temperature and time to improve photosensitivity, etc. Preferably, the baking conditions are a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds, but are not limited to this range as long as they do not impair the properties of the photosensitive resin composition of the present invention.

[0079] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed from the substrate, leaving a relief pattern on the substrate. The development method for developing the photosensitive resin layer after exposure (irradiation) can be selected from any of the conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. Furthermore, after development, a post-development bake may be performed using any combination of temperature and time, if necessary, for purposes such as adjusting the shape of the relief pattern.

[0080] The developer used for development is preferably a good solvent for the negative-type photosensitive resin composition, or a combination of the good solvent and a poor solvent. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of the good solvent and the poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative-type photosensitive resin composition. Furthermore, two or more types of solvents, for example, can be used in combination.

[0081] (4) Hardened relief pattern formation process In this process, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and the (A) polyimide precursor is imidized, thereby converting it into a cured relief pattern made of polyimide. Various methods can be selected for heat curing, such as using a hot plate, using an oven, or using a heating oven with a temperature programmable. Heating can be carried out, for example, at 170°C to 400°C for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

[0082] <Polyimide> The structure of the polyimide contained in the cured relief pattern formed from the above polyimide precursor composition is represented by the following general formula (10). [ka] {In general formula (10), X 1 and Y 1 These are the same as X1 and Y1 in general formula (1), and m is a positive integer.

[0083] The preferred X1 and Y1 in general formula (1) are also preferred in the polyimide of general formula (10) for the same reasons. The number of repeating units m in general formula (10) is not particularly limited, but may be an integer from 2 to 150. Furthermore, a method for producing polyimide that includes a step of converting the negative-type photosensitive resin composition described above into polyimide is also one aspect of the present invention.

[0084] <Semiconductor device> In this embodiment, a semiconductor device having a cured relief pattern obtained by the cured relief pattern manufacturing method described above is also provided. Therefore, a semiconductor device having a substrate which is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the cured relief pattern manufacturing method described above can be provided. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the cured relief pattern manufacturing method described above as part of the process. The semiconductor device of the present invention can be manufactured by forming the cured relief pattern formed by the cured relief pattern manufacturing method above as a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0085] <Display device> In this embodiment, a display device is provided comprising a display element and a cured film provided on the upper part of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. For example, the cured film can be a surface protective film, insulating film, and planarization film for TFT liquid crystal display elements and color filter elements, a projection for an MVA type liquid crystal display device, and a partition wall for the cathode of an organic EL element.

[0086] In addition to applications in semiconductor devices as described above, the negative-type photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coatings for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films. [Examples]

[0087] The embodiment will be described in detail below with reference to examples, but the embodiment is not limited thereto. In the examples, comparative examples, and manufacturing examples, the physical properties of the polymer or negative-type photosensitive resin composition were measured and evaluated according to the following methods.

[0088] <Measurement and Evaluation Methods> (1) Weight average molecular weight The weight-average molecular weight (Mw) of each resin was measured under the following conditions using gel permeation chromatography (on a standard polystyrene basis). Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Columns: Two Shodex KD-806M columns manufactured by Showa Denko Corporation, in series, or Showa Denko Corporation Shodex 805M / 806M in series Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko Corporation. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min

[0089] (2) Fabrication of a hardened relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a negative-type photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation), and pre-baked on a hot plate at 110°C for 180 seconds to form a coating film approximately 7μm thick. This coating film was subjected to a 500mJ / cm² test using a Prisma GHI (manufactured by Ultratech) with a test pattern mask. 2The coating was irradiated with energy. Next, the coating film was spray-developed using cyclopentanone as the developer in a coater developer (D-Spin 60A, manufactured by SOKUDO Corporation), 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 heated in a temperature-boosting programmable curing furnace (VF-2000, manufactured by Koyo Lindbergh Corporation) under a nitrogen atmosphere at the curing temperature shown in Table 1 for 2 hours to obtain a cured relief pattern on Cu consisting of resin with a thickness of approximately 4-5 μm.

[0090] (3) Evaluation of the resolution of hardened relief patterns on Cu The hardened relief patterns obtained by the above method were observed under an optical microscope, and the size of the minimum aperture pattern was determined. At this time, if the area of ​​the aperture of the obtained pattern was 1 / 2 or more of the corresponding pattern mask aperture area, it was considered resolved, and the length of the mask aperture side corresponding to the smallest resolved aperture was defined as the resolution. Resolutions of less than 10 μm were classified as "Excellent," 10 μm or more and less than 14 μm as "Good," 14 μm or more and less than 18 μm as "Acceptable," and 18 μm or more as "Unacceptable."

[0091] (4) High-temperature storage test of hardened relief patterns on Cu and subsequent evaluation of Cu surface void area A wafer on which the cured relief pattern was formed on Cu was heated in air at 150°C for 168 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh). Subsequently, the resin layer on Cu was completely removed by plasma etching using a plasma surface treatment device (EXAM model, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions were as follows. Output: 133W Gas type and flow rate: O2: 40 mL / min + CF4: 1 mL / min Gas pressure: 50 Pa Mode: Hard Mode Etching time: 1800 seconds The Cu surface, from which the resin layer had been completely removed, was observed using an FE-SEM (S-4800 model, manufactured by Hitachi High-Technologies Corporation), and the area of ​​voids on the surface of the Cu layer was calculated using image analysis software (A-zo-kun, manufactured by Asahi Kasei Corporation). When the total area of ​​voids in the negative-type photosensitive resin composition described in Comparative Example 1 was set to 100%, samples with a total void area ratio of less than 50% were judged as "Excellent," those with a ratio of 50% or more but less than 75% were judged as "Good," those with a ratio of 75% or more but less than 100% were judged as "Acceptable," and those with a ratio of 100% or more were judged as "Unacceptable."

[0092] (5) Evaluation of chemical resistance of cured relief pattern (polyimide coating) The cured relief pattern formed on Cu was immersed for 5 minutes in a resist stripping solution {ATMI Corporation, product name ST-44, main components: 2-(2-aminoethoxy)ethanol, 1-cyclohexyl-2-pyrrolidone} heated to 50°C, washed with running water for 1 minute, and air-dried. Subsequently, the film surface was visually observed with an optical microscope to evaluate chemical resistance based on the presence or absence of damage caused by the chemical solution, such as cracks, and the rate of change in film thickness after chemical treatment. As an evaluation criterion, no cracks occurred and the rate of change in film thickness was 10% or less relative to the film thickness before chemical immersion was rated "Excellent," over 10% to 15% was rated "Good," over 15% to 20% was rated "Acceptable," and cracks occurred or the rate of change in film thickness exceeded 20% was rated "Unacceptable."

[0093] (6) Adhesion test with sealing material As the epoxy encapsulant, we prepared the R4000 series manufactured by Nagase Chemtex Co., Ltd. The encapsulant was spin-coated onto an aluminum sputtered silicone wafer to a thickness of approximately 150 microns, and then heat-cured at 130°C to cure the epoxy encapsulant. On the above-mentioned epoxy cured film, the photosensitive resin composition prepared in each example and comparative example was applied to a final film thickness of 10 microns. The applied photosensitive resin composition was exposed to light at 600 mJ / cm using an aligner (PLA-501F, manufactured by Canon Corporation). 2 The entire surface was exposed with a GHI line. Then, it was heat-cured at 180°C for 2 hours to create the first layer of cured film with a thickness of 10 microns.

[0094] On the first cured layer described above, the photosensitive resin composition used to form the first cured layer was applied, and after exposing the entire surface under the same conditions as when the first cured layer was prepared, it was heat-cured to produce a second cured layer with a thickness of 10 microns. Pins were inserted into the samples prepared in the encapsulant degradation test, and adhesion tests were performed using a take-up test machine (Sebastian 5, manufactured by Quad Group). Specifically, the adhesive strength between the epoxy encapsulant and the cured relief patterns prepared from the photosensitive resin compositions prepared in each example and comparative example was measured and evaluated according to the following criteria. Rating: Adhesion strength 70 MPa or higher... Adhesion level A Adhesion strength 50 MPa or more to less than 70 MPa... Adhesion strength B Adhesion strength 30 MPa or more to less than 50 MPa... Adhesion strength C Adhesion strength less than 30 MPa... Adhesion level D

[0095] Production Example 1: (A) Synthesis of Polymer A-1 as a Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2 L separable flask, and 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature. While stirring, 81.5 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the reaction mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone was added over 60 minutes while stirring. After stirring for 2 hours at room temperature, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The obtained reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate 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 (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was found to be 20,000.

[0096] Manufacturing Example 2: (A) Synthesis of Polymer A-2 as a Polyimide Precursor The reaction was carried out in the same manner as described in Preparation Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Preparation Example 1, to obtain polymer (A-2). The weight-average molecular weight (Mw) of polymer (A-2) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 22,000.

[0097] Manufacturing Example 3: (A) Synthesis of Polymer A-3 as a Polyimide Precursor The reaction was carried out in the same manner as described in Preparation 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 Preparation Example 1, to obtain polymer (A-3). The weight-average molecular weight (Mw) of polymer (A-3) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 21,000.

[0098] Production Example 4: (A) Synthesis of Polymer A-4 as a Polyimide Precursor The reaction was carried out in the same manner as described in Preparation Example 1, except that p-phenylenediamine (50.3 g) was used instead of 4,4'-oxydianiline (ODA) as in Preparation Example 1, to obtain polymer (A-3). The weight-average molecular weight (Mw) of polymer (A-3) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 18,000.

[0099] <Example 1> Method for producing MOI-D (Compound B-1) 55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl) ether was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 77.6 g (0.50 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) mixed with 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes and stirred at room temperature for 5 hours. After that, the tetrahydrofuran was removed by distillation using a rotary evaporator to obtain compound B-1. The methacrylic equivalent of compound B-1 was 265 g / mol.

[0100] <Example 2> Method for producing MOI-AP (Compound B-2) Compound B-2 was synthesized in the same manner as in Example 1, except that 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 51.1 g (0.25 mol) of 1,4-butanediol bis(3-aminopropyl) ether. The methacrylic equivalent of compound B-2 was 257 g / mol.

[0101] <Example 3> Method for producing MOI-ODA (Compound B-3) Compound B-3 was synthesized in the same manner as in Example 1, except that 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 50.1 g (0.25 mol) of ODA. The methacrylic equivalent of compound B-3 was 255 g / mol.

[0102] <Example 4> Method for producing MOI-DEtA (Compound B-4) Compound B-4 was synthesized in the same manner as in Example 1, except that 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of diethanolamine, and 77.6 g of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol). Compound B-4 was obtained. The methacryl equivalent of compound B-4 was 260 g / mol.

[0103] <Example 5> Method for producing MOI-EG-MOI (Compound B-5) Compound B-5 was synthesized in the same manner as in Example 1, except that 77.6 g of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) was replaced with 99.6 g (0.50 mol) of 2-(2-isocyanatoethyloxy)ethyl methacrylate. The methacrylic equivalent of compound B-5 was 309 g / mol.

[0104] <Example 6> Method for producing MOI-DEA (Compound B-6) 55.1 g (0.25 mol) of N-phenyldiethanolamine was placed in a 500 mL three-necked round-bottom flask, and 100 mL of propylene glycol monomethyl ether acetate was added and stirred at room temperature. Furthermore, 77.6 g (0.50 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) was added to 150 mL of propylene glycol monomethyl ether acetate. The flask was then heated to 120°C in an oil bath, stirred at 120°C for 13 hours, and then cooled to room temperature. The propylene glycol monomethyl ether acetate was then removed using a rotary evaporator to obtain compound B-6. The methacrylic equivalent of compound B-6 was 245 g / mol.

[0105] <Example 7> Method for producing MOI-AEE (Compound B-7) Compound B-7 was synthesized in the same manner as in Example 1, except that in Production Example 5 described above, 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 (Showa Denko Co., Ltd. product name: Karenz MOI) was replaced with 38.8 g (0.25 mol). Compound B-7 was obtained. The methacryl equivalent of Compound B-7 was 260 g / mol.

[0106] <Example 8> Method for producing MOI-DOA (Compound B-8) Compound B-8 was synthesized in the same manner as in Example 1, except that 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 (Showa Denko Co., Ltd., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol). Compound B-8 was obtained. The methacryl equivalent of compound B-8 was 397 g / mol.

[0107] <Example 9> Method for producing BEI-DEtA (Compound B-9) 26.3 g (0.25 mol) of diethanolamine was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 59.8 g (0.25 mol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz BEI) mixed with 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes and stirred at room temperature for 5 hours. After that, the tetrahydrofuran was removed by distillation using a rotary evaporator to obtain compound B-9. The acrylic equivalent of compound B-9 was 172 g / mol.

[0108] <Example 10> Method for producing BEI-BHEA (Compound B-10) Compound B-10 was synthesized in the same manner as in Example 9, except that 26.3 g (0.25 mol) of diethanolamine was replaced with 37.1 g (0.25 mol) of N,N'-bis(2-hydroxyethyl)ethylenediamine, and 59.8 g (0.25 mol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate was replaced with 119.6 g (0.50 mol). Compound B-10 was obtained. The acrylic equivalent of compound B-10 was 157 g / mol.

[0109] <Example 11> (Compound B-11) 2.10 g (0.020 mol) of diethanolamine was placed in a 100 mL three-necked flask, and 5.6 g of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 2.67 g (0.021 mol) of hexyl isocyanate and 5.6 g of tetrahydrofuran was added dropwise to the flask over 15 minutes and stirred at room temperature for 4 hours. After that, the tetrahydrofuran was removed by distillation using a rotary evaporator to obtain compound B-11.

[0110] <Example 12> (Compound B-12) Compound B-12 was obtained by the same method as in Example 11, except that 2.10 g (0.020 mol) of diethanolamine was replaced with 2.10 g (0.020 mol) of 2-(2-aminoethoxy)ethanol.

[0111] <Example 13> (Compound B-13) Compound B-13 was obtained by the same method as in Example 11, except that 2.10 g (0.020 mol) of diethanolamine was replaced with 2.66 g (0.020 mol) of bis(2-methoxyethyl)amine.

[0112] <Example 14> A negative-type 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 from Example 1 as a compound, and (C) 3 g of ethanoone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, corresponding to photosensitive agent C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyllactone (GBL). The viscosity of the resulting solution was adjusted to approximately 30 poise by adding a small amount of GBL to obtain the negative-type photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

[0113] <Examples 15-26> A negative-type photosensitive resin composition similar to that in Example 14 was prepared, except that it was prepared using the mixing ratios shown in Table 1, and evaluated according to the method described above. The results are shown in Table 1.

[0114] <Example 27> Negative-type photosensitive resin compositions were prepared using polymers A-1 and A-2 by the following method, and the prepared compositions were evaluated. (A) 50 g of polymer A-1 and 50 g of polymer A-2 were used as polyimide precursors, (B) 8 g of compound B-1 was used as the compound, and (C) 3 g of ethanoone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, corresponding to photosensitive agent C-1) was used as the photopolymerization initiator, all dissolved in 150 g of γ-butyllactone (GBL). The viscosity of the resulting solution was adjusted to approximately 30 poise by adding a small amount of GBL to obtain the negative-type photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 2.

[0115] <Examples 28-36> A negative-type photosensitive resin composition similar to that in Example 14 was prepared, except that it was prepared using the mixing ratios shown in Table 2, and evaluated according to the method described above. The results are shown in Table 1.

[0116] <Example 37> A negative-type photosensitive resin composition was prepared using polymer A-3 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-3 as a polyimide precursor, (B) 8 g of compound B-1 as a compound, and (C) 3 g of ethanoone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, corresponding to photosensitive agent C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyllactone (GBL). The viscosity of the resulting solution was adjusted to approximately 30 poise by adding a small amount of GBL to obtain the negative-type photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 2.

[0117] <Example 38> A negative-type photosensitive resin composition was prepared in the same manner as in Example 24, except that polymer A-4 was used instead of polymer A-3, and evaluated according to the method described above. The results are shown in Table 2.

[0118] <Comparative Example 1> (B) A negative-type photosensitive resin composition was prepared in the same manner as in Example 1, except that compound (B) was not used, and evaluated according to the method described above. The results are shown in Table 2.

[0119] The compounds (B-1 to B-13) and photosensitive agent (C-1) listed in Table 1 are the following compounds, respectively.

[0120] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0121] C-1: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime) (Trademark: IRGACURE OXE-02 (OXE-02))

[0122] [Table 1]

[0123] [Table 2] [Industrial applicability]

[0124] By using the negative-type photosensitive resin composition according to the present invention, a cured relief pattern with high chemical resistance and resolution can be obtained, and void formation on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) Polyimide precursor represented by the following general formula (1); (B) Compounds comprising at least one selected from urethane bonds and urea bonds; and (C) Photopolymerization initiator A negative-type photosensitive resin composition containing [the specified element]. 【Chemistry 1】 {In the formula, X １ Y is a tetravalent organic group, １ is a divalent organic group, n １ is an integer between 2 and 150, and R １ and R ２ Each is independently a hydrogen atom or a monovalent organic group, R １ and R ２ At least one of them is a monovalent organic group represented by 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 of 2 to 10.}

2. The negative-type photosensitive resin composition according to claim 1, wherein the compound (B) is a compound having a urea bond.

3. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the compound (B) further comprises at least one functional group selected from a (meth)acrylic group, a hydroxyl group, an alkoxy group, and an amino group.

4. The negative-type photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) is a compound having a (meth)acrylic group and a urea bond, and the (meth)acrylic equivalent is 150 to 400 g / mol.

5. The negative-type photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) is a compound having a (meth)acrylic group and a urea bond, and the (meth)acrylic equivalent is 210 to 400 g / mol.

6. The negative-type photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) is a compound having a (meth)acrylic group and a urea bond, and the (meth)acrylic equivalent is 220 to 400 g / mol.

7. The negative-type photosensitive resin composition according to any one of claims 1 to 6, wherein the compound (B) has a structure represented by the following general formula (3). 【Transformation 3】 {In the formula, R ３ A is a hydrogen atom or a methyl group, and A is -O-, -NH-, and -NL ４ - is one of the groups selected from the group consisting of L ４ Z is a monovalent organic group having 1 to 12 carbon atoms. １ This is m with 2 to 24 carbon atoms. ２ It is a valence organic group, Z ２ It is a divalent organic group having 2 to 8 carbon atoms, and m ２ is an integer between 1 and 3.

8. The negative-type photosensitive resin composition according to any one of claims 1 to 7, wherein the compound (B) further comprises a (meth)acrylic group and at least one functional group selected from a hydroxyl group, an alkoxy group, and an amino group.

9. The negative-type photosensitive resin composition according to any one of claims 1 to 8, wherein the compound (B) is at least one compound selected from the group consisting of the following formulas (4) to (7) and (11) to (14). 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】

10. (D) A negative-type photosensitive resin composition according to any one of claims 1 to 9, further comprising a rust inhibitor.

11. The (D) rust inhibitor comprises a nitrogen-containing heterocyclic compound, as described in claim 10, for the negative-type photosensitive resin composition.

12. The negative-type photosensitive resin composition according to claim 11, wherein the nitrogen-containing heterocyclic compound is an azole compound.

13. The negative-type photosensitive resin composition according to claim 11, wherein the nitrogen-containing heterocyclic compound is a purine derivative.

14. (E) A negative-type photosensitive resin composition according to any one of claims 1 to 13, further comprising a silane coupling agent.

15. The negative-type photosensitive resin composition according to any one of claims 1 to 14, wherein X1 in the (A) polyimide precursor comprises at least one selected from the group consisting of the following general formulas (20a), (20b), and (20c). 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 {In the formula, R6 are independently a hydrogen atom, a fluorine atom, and C} １ ~C １０ The hydrocarbon group of, and C １ ~C １０ It is a monovalent group selected from the group consisting of fluorine-containing hydrocarbon groups, where l is an integer selected from 0 to 2, and m is an integer selected from 0 to 3.

16. The negative-type photosensitive resin composition according to any one of claims 1 to 15, wherein Y1 in the (A) polyimide precursor comprises at least one selected from the group consisting of the following general formulas (21a), (21b), and (21c). 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 {In the formula, R6 are independently a hydrogen atom, a fluorine atom, and C} １ ~C １０ The hydrocarbon group of, and C １ ~C １０ It is a monovalent group selected from the group consisting of fluorine-containing hydrocarbon groups, and n is an integer selected from 0 to 4.

17. The (A) polyimide precursor is the following general formula (8): [Chemistry 18] {In the formula, n １ is an integer between 2 and 150, and R １ and R ２ Each of these is independently either a hydrogen atom or a monovalent organic group. A negative-type photosensitive resin composition according to any one of claims 1 to 16, comprising a polyimide precursor having a structural unit represented by .

18. The (A) polyimide precursor is the following general formula (9): 【Chemistry 19】 {In the formula, n １ is an integer between 2 and 150, and R １ and R ２ Each of these is independently either a hydrogen atom or a monovalent organic group. A negative-type photosensitive resin composition according to any one of claims 1 to 17, comprising a polyimide precursor having a structural unit represented by .

19. The (A) polyimide precursor is the following general formula (8): 【Chemistry 20】 {In the formula, n １ is an integer between 2 and 150, and R １ and R ２ Each is independently a hydrogen atom or a monovalent organic group, and R in general formula (9) １ , R ２ , and n １ It may be the same as, or different from. A structural unit represented by, The following general formula (9): 【Chemistry 21】 {In the formula, n １ is an integer between 2 and 150, and R １ and R ２ Each is independently a hydrogen atom or a monovalent organic group, and R in general formula (8) １ , R ２ , and n １ It may be the same as, or different from. It is a copolymer with structural units represented by, or A negative-type photosensitive resin composition according to any one of claims 1 to 18, which is a mixture of a polyimide precursor having a structural unit represented by the above general formula (8) and a polyimide precursor having a structural unit represented by the above general formula (9).

20. The negative-type photosensitive resin composition according to claim 19, wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formula (8) and a structural unit represented by the general formula (9).

21. 100 parts by mass of the (A) polyimide precursor, Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) compound and Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator and A negative-type photosensitive resin composition according to any one of claims 1 to 20, comprising the above.

22. A method for producing polyimide, comprising the step of converting a negative-type photosensitive resin composition according to any one of claims 1 to 21 into a polyimide.

23. (1) A step of applying the negative-type photosensitive resin composition according to any one of claims 1 to 21 onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element].

24. A compound represented by the following formula (5). 【Chemistry 22】

25. A compound represented by the following formula (6). 【Chemistry 23】

26. A compound represented by the following formula (7). 【Chemistry 24】

27. A compound represented by the following formula (11). 【Chemistry 25】

28. A compound represented by the following formula (12). 【Chemistry 26】

29. A compound represented by the following formula (13). 【Chemistry 27】

30. A compound represented by the following formula (14). 【Chemistry 28】

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