Negative-type photosensitive resin composition, method for producing polyimide, method for producing cured relief pattern, and semiconductor device.

Abstract

The present invention provides a negative-type photosensitive resin composition that exhibits good resolution even when there is a shift in the depth of focus, has good adhesion to the molding resin, and exhibits a low dielectric constant; a method for producing polyimide using the photosensitive resin composition; a method for producing a cured relief pattern; and a semiconductor device having the cured relief pattern. [Solution] A negative-type photosensitive resin composition characterized by comprising (B) a polyimide precursor containing a structure represented by general formula (A1), and (C) a photopolymerization initiator and a solvent. TIFF2026069582000131.tif60150

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive resin composition used, for example, as an insulating material for electronic components and for forming relief patterns such as passivation films, buffer coat films, and interlayer insulating films in semiconductor devices, as well as a method for producing polyimide using the same, a method for producing a cured relief pattern, and a semiconductor device. [Background technology]

[0002] <<First Background Technology>> Conventionally, polyimide resins possessing excellent heat resistance, electrical properties, and mechanical properties have been used as insulating materials for electronic components, as well as for passivation films, surface protective films, and interlayer insulating films of semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursor 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 polyimide precursor compositions have the advantage of enabling a significant reduction in process steps compared to conventional non-photosensitive polyimide 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, with the increasing speed of devices and the fact that operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting now 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 top of it, and then the chip is flipped over and directly mounted on a printed circuit board. Because the wiring distance can be precisely controlled with this flip-chip mounting, it has been adopted for high-end devices that handle high-speed signals, and also for mobile phones and other devices due to its small mounting size, and demand is rapidly expanding. More recently, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a wafer that has undergone pre-processing, the individual chips are reconstructed on a support and sealed with molding resin, and then the redistribution layer is formed after peeling off the support (for example, Patent Document 1). Fan-out wafer-level packaging has the advantages of being able to reduce the height of the package, as well as enabling high-speed transmission and cost reduction.

[0005] ≪Second Background Technology≫

[0006] 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.

[0007] 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, with the increasing speed of devices and the fact that operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting now 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.

[0008] 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 2). Because the wiring distance can be precisely controlled in this flip-chip mounting, it has been adopted for high-end devices that handle high-speed signals, and 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 to a thickness of 1 μm or less to serve as a seed layer for plating, and then 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.

[0009] Furthermore, fan-out type semiconductor packages have been attracting attention in recent years. 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 encapsulating material (resin layer). In addition, a redistribution layer is formed that extends to the area of ​​the semiconductor chip and the encapsulating material. The redistribution layer is formed with a thin film thickness. Moreover, because the redistribution layer can be formed in the area of ​​the encapsulating material, the number of external connection terminals can be increased. For such a metal rewiring layer, it is required that the adhesion between the rewired metal layer and the resin layer be high after reliability tests. In particular, in recent years, it has been required that the temperature for heat-curing the rewiring layer be lower. Examples of reliability tests include a high-temperature storage test in which, for example, it 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, while wiring is assembled and voltage is applied, its operation is confirmed under storage in air at a temperature of about 125°C for 100 hours or more; a temperature cycle test in which it is cycled between a low-temperature state of about -65°C to -40°C and a high-temperature state of about 125°C to 150°C in air; a high-temperature and high-humidity storage test in which it is stored in a water vapor atmosphere at a temperature of 85°C or higher and a humidity of 85% or higher; a high-temperature and high-humidity bias test in which the same test as the high-temperature and high-humidity storage test is performed while wiring is assembled and voltage is applied; and a solder reflow test in which it is passed through a solder reflow furnace at 260°C a plurality of times in air or under nitrogen, etc.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0011] ≪First Problem≫ However, in recent years, due to the diversification of package mounting technologies, the types of supports have diversified, and in addition, the rewiring layer has become multilayered. Therefore, when exposing a photosensitive resin composition, there have been problems such as a deviation in the depth of focus, resulting in a significant deterioration in resolution, or a significant difference in the resolution obtained depending on the difference in the base substrate. Also, in the case of a fan-out package, adhesion to a mold resin composed of an epoxy resin, etc. is required. However, in a conventional negative photosensitive resin composition, there has been a problem that the yield decreases when made into a package because there is not enough adhesion. Furthermore, while there has been a growing demand for low dielectric constant materials in recent years, conventional materials still had room for improvement.

[0012] The present invention aims to provide a negative-type photosensitive resin composition that exhibits good resolution even when there is a shift in the depth of focus, has good adhesion to the molding resin, and exhibits a low dielectric constant; a method for producing polyimide using the photosensitive resin composition; a method for producing a cured relief pattern; and a semiconductor device having the cured relief pattern.

[0013] ≪Second Challenge≫ However, in conventional reliability tests, particularly high-temperature storage tests, a problem arose where voids formed at the interface between the rewired Cu layer and the resin layer after the test. This tendency was especially pronounced when the heat curing temperature was low. When voids form at the interface between the Cu layer and the resin layer, the adhesion between the two decreases.

[0014] In addition to the void problem, metal redistribution layers are required to have 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 the generation of voids and exhibit high chemical resistance and resolution.

[0015] The present invention was devised in view of the above-mentioned conventional circumstances, and one of its objectives is to provide a negative-type photosensitive resin composition (hereinafter also 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. [Means for solving the problem]

[0016] <Means for solving the first problem> The inventors have discovered that the above objective can be achieved by combining a specific polyimide precursor with a specific photopolymerization initiator, and have completed the present invention. That is, the present invention is as follows. [1] A negative-type photosensitive resin composition comprising (A) a polyimide precursor having an unsaturated double bond in its side chain, and (B) a photopolymerization initiator having an oxime structure, The IR spectrum when (A) is heated and cured at 230°C is (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500cm) -1 The absorption peak values ​​in the vicinity are 0.1 to 0.56. Add 100 mJ / cm³ to the 100 μM dimethyl sulfoxide solution of (B) mentioned above. 2 A negative-type photosensitive resin composition characterized by having a radical generation amount of 3.0 to 30.0 μM when irradiated with a light source. [2] The aforementioned (1380cm) -1 (Absorption peak value in the vicinity) / (1500cm) -1 The negative-type photosensitive resin composition according to [1], wherein the absorption peak value in the vicinity is 0.3 to 0.54. [3] The negative-type photosensitive resin composition according to [1] or [2], wherein the radical generation amount is 5.0 to 30.0 μM. [4] A negative-type photosensitive resin composition according to any one of [1] to [3], wherein the radical generation amount is 8.0 to 30.0 μM. [5] A negative-type photosensitive resin composition according to any one of [1] to [4], wherein the radical generation amount is 10.0 to 30.0 μM. [6] A negative-type photosensitive resin composition according to any one of [1] to [5], further comprising (C) a solvent. [7] The polyimide precursor having an unsaturated double bond in the side chain (A) is given by the following general formula (A1): [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] A negative-type photosensitive resin composition according to any one of [1] to [6], comprising a structure represented by {(in general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms at the same time.}. [8] In the above general formula (A1), Y is given by the following general formula (Y1): [ka] (In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms, which may contain a halogen atom; a represents an integer from 0 to 4; A independently represents an oxygen atom or a sulfur atom; and B is given by the following formula: [ka] A negative-type photosensitive resin composition according to [[7]], comprising a structure represented by ). [9] A negative-type photosensitive resin composition according to any one of [1] to [8], wherein the weight-average molecular weight (Mw) of (A) is 15,000 to 38,000.

[10] In the above general formula (A1), Y is given by the following formula: [ka] Or the following formula: [ka] A negative-type photosensitive resin composition according to any one of [7] to [9], having a structure represented by [the formula shown].

[11] In the above general formula (A1), X is given by the following general formula (X1): [ka] (In the formula, Ry represents a monovalent organic group having 1 to 10 carbon atoms, which may each independently contain a halogen atom; a represents an integer from 0 to 4; C is at least one selected from the group consisting of a single bond, an ester bond, an oxygen atom, and a sulfur atom; and D is a single bond, or the following formula: [ka] A negative-type photosensitive resin composition according to any one of [7] to

[10] , comprising a structure represented by )].

[12] In general formula (X1), C is an oxygen atom or a sulfur atom, and D is given by the following formula: [ka] A negative-type photosensitive resin composition according to

[11] , comprising at least one of the following.

[13] The above X is given by the following formula: [ka] Or the following formula: [ka] A negative-type photosensitive resin composition according to any one of [7] to

[12] , having a structure represented by [7].

[14] A negative-type photosensitive resin composition according to any one of [7] to

[13] , wherein p in the general formula (R1) is 3 to 10.

[15] A negative-type photosensitive resin composition according to any one of [7] to

[14] , wherein the cured film, which has been heat-cured at 230°C for 2 hours, has a weight loss rate of 0.5 to 3.0% when heated at 350°C, and the proportion of the weight loss component derived from R1 and R2 in the general formula (A1) is 60 to 80%.

[16] The following general formula (A1): [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] The structure is represented by {(In the general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) and is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms at the same time.}, where Y is represented by the following general formula (Y1): [ka] (In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms, which may contain a halogen atom; a represents an integer from 0 to 4; A is an oxygen atom or a sulfur atom; and B is given by the following formula: [ka] (A) A polyimide precursor containing a structure represented by ) ] A negative-type photosensitive resin composition characterized by comprising (B) a photopolymerization initiator having an oxime structure and (C) a solvent.

[17] The negative-type photosensitive resin composition according to

[16] , wherein the weight-average molecular weight (Mw) of (A) is 15,000 to 38,000.

[18] In the above general formula (A1), Y is given by the following formula: [ka] Or the following formula: [ka] A negative-type photosensitive resin composition according to either

[16] or

[17] , having the structure shown.

[19] The IR spectrum when (A) is heated and cured at 230°C is (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500cm) -1 The absorption peak values ​​in the vicinity are 0.1 to 0.56. Add 100 mJ / cm³ to the 100 μM dimethyl sulfoxide solution of (B) mentioned above. 2 A negative-type photosensitive resin composition according to any one of

[16] to

[18] , wherein the amount of radicals generated when irradiated is 3.0 to 30.0 μM.

[20] The following general formula (A1): [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] The structure is represented by {(in the general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.)}, where X is the following general formula (X1): [ka] (In the formula, Ry represents a monovalent organic group having 1 to 10 carbon atoms, which may each independently contain a halogen atom; a represents an integer from 0 to 4; C is at least one selected from the group consisting of a single bond, an ester bond, an oxygen atom, and a sulfur atom; and D is a single bond, or the following formula: [ka] A polyimide precursor containing the structure represented by ) is one of the types within it. A negative-type photosensitive resin composition characterized by containing (B) a photopolymerization initiator having an oxime structure and (C) a solvent. [twenty one] In the general formula (X1), C is an oxygen atom or a sulfur atom, and D is the following formula: [Chemical formula] The negative photosensitive resin composition according to

[20] , wherein D is one of the following:

[22] X is the following formula: [Chemical formula] Or the following formula: [Chemical formula] The negative photosensitive resin composition according to

[20] or

[21] , which is represented by the structure shown above.

[23] When the (A) is heat-cured at 230 °C, the ratio of the absorption peak value near 1380 cm -1 to the absorption peak value near 1500 cm -1 in the IR spectrum is 0.1 to 0.56, and when the 100 μM dimethyl sulfoxide solution of (B) is irradiated with 100 mJ / cm 2 , the amount of radicals generated is 3.0 to 30.0 μM. The negative photosensitive resin composition according to any one of

[20] to

[22] .

[24] The photoinitiator having an oxime structure of (B) is the following general formula (B): [Chemical formula] (In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents an organic group having 1 to 20 carbon atoms, Rc represents an organic group having 1 to 10 carbon atoms, Rd represents an organic group having 1 to 10 carbon atoms, and b is an integer of 0 to 2. Rg represents an organic group having 1 to 4 carbon atoms, and a plurality of Rg may form a ring.) Or the general formula (B1): [Chemical formula] (In the formula, Re represents a monovalent organic group with 1 to 20 carbon atoms, and Rf represents an organic group with 1 to 10 carbon atoms.) A negative-type photosensitive resin composition according to any one of [1] to

[23] , comprising a structure represented by [1]. [twenty five] The negative-type photosensitive resin composition according to any one of [6] to

[24] , wherein the solvent (C) is at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

[26] The negative-type photosensitive resin composition according to any one of [6] to

[25] , wherein the solvent (C) is at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

[27] A negative-type photosensitive resin composition according to any one of [1] to

[26] , further comprising (D) a polymerization inhibitor.

[28] A method for producing polyimide, comprising curing a negative-type photosensitive resin composition described in any of [1] to

[27] .

[29] The following steps: (1) A coating step of applying a negative-type photosensitive resin composition described in any of [1] to

[27] onto a substrate to form a photosensitive resin layer on the substrate, (2) An exposure step of exposing the photosensitive resin layer, (3) A developing step in which the photosensitive resin layer after exposure is developed to form a relief pattern, (4) A heating step to form a hardened relief pattern by heat treatment of the relief pattern, A method for producing a hardened relief pattern, characterized by including [a specific element].

[30] A semiconductor device having a cured relief pattern obtained by the manufacturing method described in

[29] .

[31] The following general formula (A1); [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] A monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, represented by the general formula (R1): {In general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} However, R1 and R2 cannot both be hydrogen atoms at the same time. A cured film obtained by curing a polyimide precursor containing the structure represented by ] A cured film having a weight loss rate of 0.5 to 3.0% when heated at 350°C, wherein the proportion of the weight loss component derived from R1 and R2 in the general formula (A1) is 60 to 80%.

[32] The following general formula (A1); [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] A monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, represented by the general formula (R1): {In general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} However, R1 and R2 cannot both be hydrogen atoms at the same time. A cured film obtained by curing a polyimide precursor containing the structure represented by ] The concentration of imide groups in the polyimide in the cured film is 12.0% to 25.0%, A cured film having a weight loss rate of 0.5 to 3.0% when heated at 350°C.

[33] IR spectrum (1380 cm) -1 (Absorption peak value in the vicinity) / (1500cm) -1 The cured film described in

[31] , wherein the absorption peak value in the vicinity is 0.3 to 0.54.

[34] A cured film according to any one of

[31] to

[33] , wherein the dielectric loss tangent at 10 GHz is 0.001 to 0.009.

[35] The following general formula (A1); [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] A monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, represented by the general formula (R1): {In general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} However, R1 and R2 cannot both be hydrogen atoms at the same time. A cured film obtained by curing a polyimide precursor containing the structure represented by ] The concentration of imide groups in the polyimide in the cured film is 12.0% to 25.0%, A method for manufacturing a cured film, wherein the weight loss rate of the cured film when heated at 350°C is 0.5 to 3.0%, A coating process that forms a film containing a photosensitive polyimide precursor. A curing step to polyimide a film containing the polyimide precursor. Having at least, The curing step includes a heating step at 150 to 250°C, and is a method for producing a polyimide cured film.

[0017] <Means for solving the second problem> The inventors of the present invention have discovered that the above problems can be solved by combining a specific polyimide precursor, a silane coupling agent having a specific structure, and a specific organic solvent, and have completed the present invention. That is, the present invention is as follows. [1] The following ingredients: (A) Polyimide precursor; (B) Photopolymerization initiator; (C) General formula (1): [ka] {In the formula, a is an integer from 1 to 3, n is an integer from 1 to 6, and R 21 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 22 R is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and 20 This is at least one substituent selected from the group consisting of an epoxy group, a phenylamino group, a ureido group, and an isocyanate group. Silane coupling agents represented by; and (D) An organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone; A negative-type photosensitive resin composition containing [the specified element]. [2] In the above general formula (1), R 20The negative-type photosensitive resin composition according to [1], wherein is at least one selected from the group consisting of substituents comprising a phenylamino group and a ureido group. [3] In the above general formula (1), R 20 A negative-type photosensitive resin composition according to [1] or [2], wherein the substituent contains a phenylamino group. [4] (E) A negative-type photosensitive resin composition according to any one of [1] to [3], further comprising a thermobase generator. [5] The negative-type photosensitive resin composition according to any one of [1] to [4], wherein the (D) organic solvent contains at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, and ε-caprolactone. [6] The aforementioned (A) polyimide precursor is given by the following general formula (2): [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 each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a monovalent organic group.} A negative-type photosensitive resin composition according to any one of [1] to [5], having a structural unit represented by . [7] In the above general formula (2), at least one of R1 and R2 is given by the following general formula (3): [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.} A negative-type photosensitive resin composition according to [6], wherein the monovalent organic group is represented by . [8] In the above general formula (2), X1 is given by the following general formula (20a): [ka] A negative-type photosensitive resin composition according to [6] or [7], having a structure represented by [6]. [9] In the above general formula (2), X1 is given by the following general formula (20b): [ka] A negative-type photosensitive resin composition according to [6] or [7], having a structure represented by [6].

[10] In the above general formula (2), X1 is given by the following general formula (20c): [ka] A negative-type photosensitive resin composition according to [6] or [7], having a structure represented by [6].

[11] In the above general formula (2), Y1 is given by the following general formula (21b): [ka] A negative-type photosensitive resin composition according to any one of [6] to

[10] , comprising a structure represented by .

[12] In the above general formula (2), Y1 is given by the following general formula (21c): [ka] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} A negative-type photosensitive resin composition according to any one of [6] to

[10] , comprising a structure represented by .

[13] The aforementioned (A) polyimide precursor is the following general formula (4): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150.} A negative-type photosensitive resin composition according to [6] or [7], having a structural unit represented by .

[14] The aforementioned (A) polyimide precursor is the following general formula (5): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150.} A negative-type photosensitive resin composition according to [6] or [7], having a structural unit represented by .

[15] The aforementioned (A) polyimide precursor is the following general formula (4): [ka] The structural unit represented by {wherein R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150}, The following general formula (5): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150. These may be the same as or different from R1, R2, and n1 in general formula (4).} A negative-type photosensitive resin composition according to [6] or [7], which simultaneously includes a structural unit represented by .

[16] The negative-type photosensitive resin composition according to

[15] , wherein the (A) polyimide precursor is a copolymer of structural units represented by the general formulas (4) and (5).

[17] The aforementioned (A) polyimide precursor is the following general formula (6): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150.} A negative-type photosensitive resin composition according to [6] or [7], having a structural unit represented by .

[18] 100 parts by mass of the (A) polyimide precursor, Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (B) photopolymerization initiator and Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) silane coupling agent and A negative-type photosensitive resin composition according to any one of [1] to

[17] , comprising the above.

[19] A method for producing polyimide, comprising the step of converting a negative-type photosensitive resin composition described in any of [1] to

[18] into a polyimide.

[20] The following steps: (1) A step of applying a negative-type photosensitive resin composition described in any of [1] to

[18] 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; and, (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]. [Effects of the Invention]

[0018] <<Effects of the First Invention>> According to the present invention, it is possible to provide a negative-type photosensitive resin composition that exhibits good resolution even when there is a shift in the depth of focus, has good adhesion to the molding resin, and exhibits a low dielectric constant, a method for producing polyimide using the photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device having the cured relief pattern.

[0019] ≪Effects of the second invention≫ According to the present invention, it is possible to provide a negative-type photosensitive resin composition and a method for producing polyimide that can obtain high chemical resistance and resolution, and suppress the generation of voids at the interface of the Cu layer in contact with the resin layer after high-temperature storage testing, and a method for forming a cured relief pattern using the negative-type photosensitive resin composition. [Modes for carrying out the invention]

[0020] ≪Modes for Carrying Out the First Invention≫ This embodiment will be described in detail below. Throughout this specification, structures represented by the same symbols in a general formula may be identical or different from each other if multiple such structures exist in the molecule.

[0021] <Photosensitive resin composition> The photosensitive resin composition according to this embodiment contains (A) a polyimide precursor of a specific structure, (B) a photopolymerization initiator of a specific structure, and (C) a solvent. Furthermore, the photosensitive resin composition of the present invention preferably further contains (D) a polymerization inhibitor in addition to the above components. Such a photosensitive resin composition makes it possible to obtain a cured relief pattern that exhibits good focus margin, resolution, good adhesion to the molding resin, and low dielectric constant.

[0022] [(A) Polyimide precursor] The (A) polyimide precursor according to this embodiment will be described below. The (A) polyimide precursor according to this embodiment has an unsaturated double bond in its side chain, and in the IR spectrum of the cured film obtained by heat curing at 230°C, (1380 cm⁻¹) -1 (Absorption peak value in the vicinity) / (1500cm) -1 The absorption peak value in the vicinity is not limited as long as it is between 0.1 and 0.56. By using such a polyimide precursor, a negative-type photosensitive resin composition can be obtained that exhibits good resolution, excellent adhesion to molding resin, and a low dielectric constant.

[0023] The IR spectrum was measured using the method described in the examples below, and the peak values ​​were ±10 cm from each wavenumber. -1 Within the specified range, the largest peak value is defined as the peak value. Among these, from the viewpoint of exhibiting a low dielectric constant, a value of 0.54 or less is more preferable, and 0.50 or less is particularly preferable. Furthermore, from the viewpoint of developability, a value of 0.2 or more is preferable, and 0.3 or more is more preferable.

[0024] The (A) polyimide precursor according to this embodiment is the following general formula (A1) [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] It is preferable to include a structure represented by {(In general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms at the same time.}.

[0025] Y is not limited to any divalent organic group, but is preferably an organic group having 6 to 60 carbon atoms, and more preferably contains an aromatic ring having 18 to 60 carbon atoms, and is given the following general formula (Y1): [ka] (In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms, which may contain a halogen atom, and a represents an integer from 0 to 4. A independently represents an oxygen atom or a sulfur atom, and B is given by the following formula: [ka] It is one of the types.) [ka] It is more preferable that the formula includes (wherein Rz independently represents a monovalent organic group having 1 to 10 carbon atoms, which may each contain a halogen atom, a represents an integer from 0 to 4, and A independently represents either an oxygen atom or a sulfur atom).

[0026] From the viewpoint of achieving a low dielectric constant, Y is preferably a structure represented by the general formula (Y1), and from the viewpoint of focus margin and adhesion to the mold resin, it is preferably one of the following structures. [ka] [ka] [ka]

[0027] The following structures can be given as examples of structures represented by the general formula (Y2). [ka] [ka] [ka] [ka]

[0028] Furthermore, the above general formula (Y1) may also include the following structure. [ka] [ka] The structure may include each of the following: {In the above formula, A is a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), or a butyl group (-C4H9).}

[0029] In the above general formula (R1), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitivity. p is preferably an integer between 2 and 10 from the viewpoint of photosensitivity, and more preferably an integer between 2 and 4.

[0030] In the above general formula (A1), the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, and more preferably a tetravalent aromatic group or an alicyclic aliphatic group in which one of the -COOR1 group and the -CONH- group is bonded to the same aromatic ring and both are in the ortho position relative to each other. In the former case, the aromatic ring to which the -COOR1 group is bonded and the aromatic ring to which the -COOR2 group is bonded may be the same aromatic ring or may be different aromatic rings. In this context, the aromatic ring is preferably a benzene ring.

[0031] A more preferable tetravalent organic group represented by X is the following: [ka] [ka] {In the formula, n represents an integer between 5 and 20 (inclusive).} Examples of structures that can be represented by each of these are, but are not limited to, these. Also, the structure of X can be one type or a combination of two or more types.

[0032] In particular, in the photosensitive resin composition of the present invention, the tetravalent organic group represented by X in the above general formula (A1) has the following structure: [ka] Or the following structure: [ka] It is particularly preferable that it includes [this]. (A) The polyimide precursor having such a structure improves the heat resistance and photosensitivity of the negative-type photosensitive resin composition, and improves the focus margin and chemical resistance of the resulting cured relief pattern.

[0033] Furthermore, (A) the polyimide precursor is defined as follows: In the above general formula (Y1), X is the following general formula (X1): [ka] (In the formula, Ry represents a monovalent organic group having 1 to 10 carbon atoms, which may each independently contain a halogen atom; a represents an integer from 0 to 4; C is at least one selected from the group consisting of a single bond, an ester bond, an oxygen atom, and a sulfur atom; and D is a single bond, or the following formula: [ka] It is one of the types. It is preferable to do so.

[0034] In particular, in general formula (X1), C is an oxygen atom or a sulfur atom, and D is given by the following formula: [ka] It is even more preferable that it be one of the types included.

[0035] In the negative-type photosensitive resin composition of the present invention, in the above general formula (A1), X has the following structure: [ka] Includes, Y has the following structure: [ka] It is most preferable to include [this]. (A) The polyimide precursor having such a structure further improves the heat resistance and photosensitivity of the negative-type photosensitive resin composition, improving the focus margin and exhibiting a low dielectric constant in the resulting cured relief pattern.

[0036] In particular, in the present invention, in the polyimide precursor (A), the diamine-derived skeletal component Y has a structure represented by the general formula (Y1) described above, that is, a structure in which four phenyl rings are bonded, thereby enabling the creation of a low dielectric loss tangent (Df) for the resulting cured relief pattern. In the resulting hardened relief pattern, the dielectric loss tangent (Df) is preferably less than 0.009, more preferably less than 0.0085, and even more preferably less than 0.008 at 10 GHz.

[0037] [(A) Method for preparing polyimide precursors] The above-mentioned ester-linked polyimide precursor is obtained, for example, by first reacting a tetracarboxylic dianhydride having a desired tetravalent organic group X with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester). Subsequently, this acid / ester is obtained by amide polycondensation with a diamine having a divalent organic group Y. In addition to the alcohol having the above-mentioned photopolymerizable group, saturated aliphatic alcohols may optionally be used in combination.

[0038] (Preparation of acid / ester compounds) In the present invention, suitable tetracarboxylic dianhydrides having a tetravalent organic group X for preparing ester-linked polyimide precursors include, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, and diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride. Examples of such compounds include, but are not limited to, acidic dianhydrides, diphenylmethane-3,3',4,4'-tetracarboxylic acid dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidene diphenoxy)phthalic anhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride. These compounds can be used individually or in combination of two or more.

[0039] In the present invention, suitable photopolymerizable alcohols used to prepare ester-linked polyimide precursors include, for example, 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 rilate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 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.

[0040] In addition to the alcohols having the above-mentioned photopolymerizable groups, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferably used as optional saturated aliphatic alcohols. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like.

[0041] By stirring and mixing the tetracarboxylic dianhydride suitable for the present invention and the above alcohols in a suitable reaction solvent, preferably in the presence of a basic catalyst such as pyridine, at a temperature of 20 to 50°C for 4 to 10 hours, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0042] The reaction solvent described above is preferably one that completely dissolves the starting materials, tetracarboxylic dianhydride and alcohols, as well as the resulting acid / ester product. More preferably, the solvent is one that also completely dissolves the polyimide precursor, which is the amide polycondensation product of the acid / ester product and the diamine. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. Specific examples of these include: Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Examples of esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate;

[0043] Examples of lactones include γ-butyrolactone; Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc. Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc. Examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene, etc. These can be listed individually or in combination of two or more, as needed.

[0044] (Preparation of polyimide precursors) To the above acid / ester mixture (typically in solution in the above reaction solvent), preferably under ice cooling, a suitable dehydrating condensation agent is added and mixed to convert the acid / ester mixture into a polyacid anhydride. Then, diamines having a divalent organic group Y, which are preferably used in the present invention, are added dropwise after being dissolved or dispersed in a separate solvent, and the two are subjected to amide polycondensation to obtain the desired polyimide precursor. Diaminosiloxanes may also be used in combination with the above diamines having a divalent organic group Y. Examples of the above-mentioned dehydration condensing agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. As described above, the intermediate polyacid anhydride is obtained.

[0045] In the present invention, diamines having a divalent organic group Y that are suitably used in reaction with the polyacid anhydride obtained as described above include, for example, 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane, bis{4-(4-aminophenoxy)phenyl}sulfone, bis{4-(3-aminophenoxy)phenyl}sulfone, bis{4-(4-aminophenoxy)phenyl}ketone, and 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane. In addition to the above, the following diamines may be used, provided they do not cause adverse effects. p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,

[0046] 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, etc. and those in which some of the hydrogen atoms on these benzene rings are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogen atoms, etc. This also includes mixtures thereof.

[0047] Diaminosiloxanes are used in combination with diamines containing the divalent organic group Y in the preparation of (A) the photosensitive polyimide precursor, for the purpose of improving the adhesion between the coating film formed from the photosensitive resin composition of the present invention and various substrates. Specific examples of such diaminosiloxanes include, for example, 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane.

[0048] 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 suitable poor solvent (e.g., water, aliphatic lower alcohol, or a mixture thereof) is added to the solution containing the polymer components to precipitate the polymer components. Further purification of the polymer is carried out by repeating operations such as redissolution and reprecipitation as needed, and then the target polyimide precursor is isolated by vacuum drying. 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.

[0049] The weight-average molecular weight of the ester-bonded polyimide precursor is preferably 1,000 or more, more preferably 5,000 or more, as measured by gel permeation chromatography in terms of polystyrene equivalent, from the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in the developer, the weight-average molecular weight is more preferably 50,000 or less. (A) The weight-average molecular weight (Mw) of the polyimide precursor is even more preferably 15,000 to 38,000. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the developing solvent for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

[0050] [(B) Photopolymerization initiator] The photopolymerization initiator (B) in this embodiment is a 100 μM solution of dimethyl sulfoxide (DMSO) exposed to a 365 nm UV lamp at 100 mJ / cm². 2 The amount of radicals generated upon irradiation is 3.0 to 30.0 μM. The amount of radicals generated in this embodiment can be calculated using the method described in the examples below. The photopolymerization initiator (B) in this embodiment is not limited as long as the radical generation amount is 3.0 to 30.0 μM. Being within this range prevents degradation of the mold resin and provides excellent adhesion between the mold resin and the cured relief pattern. From the viewpoint of focus margin, 5.0 to 30.0 μM is preferred, 8.0 to 30.0 μM is more preferred, and 10.0 to 30.0 μM is even more preferred.

[0051] In this embodiment, the reason why good adhesion between the mold resin and the cured relief pattern occurs when the amount of radical generation is within the above range is not clear, but the inventors have hypothesized the following. This embodiment is a negative-type photosensitive resin composition containing a polyimide precursor having unsaturated double bonds in its side chains and a photopolymerization initiator having an oxime structure. Radicals generated from the initiator react with the double bonds in the side chains, causing the material to develop, and it is subsequently converted to polyimide by thermal curing.

[0052] Here, when the double bonds of the side chain react, at low temperatures such as 230°C, the conversion to polyimide tends not to be completed, and some of the side chain remains. It is presumed that this allows for reactions such as transesterification with the hydroxyl groups formed by the partial ring-opening of the epoxy groups of the molding resin, thereby improving adhesion. In particular, at concentrations of 5 μM or higher, the reaction of the double bonds of the side chain occurs sufficiently, resulting in improved adhesion. Furthermore, it is estimated that when the amount of radical generation exceeds 30 μM, the large amount of radical generation causes recombination between initiators, preventing crosslinking between side chains. As a result, the recombined initiator molecules form a fragile layer at the interface between the mold resin and the polyimide, leading to a decrease in adhesion. In this embodiment, a photopolymerization initiator whose radical generation amount falls within the above range can be achieved by appropriately selecting the structure of the compound. Photopolymerization initiators are generally thought to absorb irradiated light (wavelength 365 nm in this embodiment), enter an excited state, and then either cleave themselves to generate radicals, or extract hydrogen from other molecules to generate radicals. Therefore, in order to keep the above range, for example, if you want to increase the amount of radical generation, you can increase the amount of light absorbed at 365 nm by increasing the molar extinction coefficient at 365 nm, thereby adjusting the amount of radical generation. In terms of chemical structure, one method is to shift the absorption maximum to the longer wavelength side and increase the molar extinction coefficient by using a structure that contains heteroatoms, and a heterocyclic compound containing heteroatoms is particularly effective. Furthermore, to reduce radical generation, the amount of light absorbed at 365 nm can be lowered by reducing the molar extinction coefficient at 365 nm, thereby adjusting the amount of radical generation. In terms of chemical structure, it is effective to remove substituents containing heteroatoms from the chemical structure.

[0053] In this embodiment, the photopolymerization initiator (B) is preferably a structure having an oxime structure and further containing a heteroatom, and more preferably a structure represented by the following general formula (B) or general formula (B1). [ka] (In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents an organic group having 1 to 20 carbon atoms, Rc represents an organic group having 1 to 10 carbon atoms, Rd represents an organic group having 1 to 10 carbon atoms, b is an integer from 0 to 2, and Rg represents an organic group having 1 to 4 carbon atoms, and multiple Rg groups may form a ring.) [ka] (In the formula, Re represents a monovalent organic group with 1 to 20 carbon atoms, and Rf represents a monovalent organic group with 1 to 10 carbon atoms.)

[0054] In general formula (B), Ra is not limited to any monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of heat resistance, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, ethyl group, or propyl group is more preferred. Rb is not limited to any organic group having 1 to 20 carbon atoms, but from the viewpoint of resolution, a monovalent organic group derived from an aromatic group having 6 to 20 carbon atoms or a heterocyclic compound having 5 to 20 carbon atoms is preferred. Rc is not limited to any organic group having 1 to 10 carbon atoms. Among these, a monovalent organic group containing a saturated alicyclic structure with 3 to 10 carbon atoms is more preferred from the viewpoint of resolution. Rd is not limited to any organic group having 1 to 10 carbon atoms. Among these, organic groups having 1 to 3 carbon atoms are preferred from the viewpoint of resolution, and methyl, ethyl, and propyl groups are more preferred.

[0055] In general formula (B1), Re is not limited to any monovalent organic group having 1 to 20 carbon atoms. Among these, it is preferable that it contains a saturated hydrocarbon group from the viewpoint of chemical resistance. Rf is not limited to any organic group having 1 to 10 carbon atoms. Among these, organic groups having 1 to 3 carbon atoms are preferred from the viewpoint of resolution, and methyl, ethyl, and propyl groups are more preferred.

[0056] In the negative-type photosensitive resin composition according to this embodiment, the adhesion between the resulting cured relief pattern (polyimide resin) and the mold resin is improved by including the structure of (B) or (B1) in the photopolymerization initiator (B). The reason for this is not clear, but the inventors believe it to be as follows. In other words, epoxy resins are generally used as mold resins, and some epoxy moieties of the epoxy resin remain in the form of ring-opened hydroxyl groups. The (A) polyimide precursor according to this embodiment has two or more oxygen atoms or sulfur atoms, and by including the (B) photopolymerization initiator of the above structure, we believe that the nitrogen atoms or sulfur atoms remaining after radical generation of the photopolymerization initiator improve the adhesion between the hydroxyl groups remaining in the mold resin and the polyimide resin.

[0057] (C) Solvent The solvent (C) according to this embodiment is not limited to any solvent that can uniformly dissolve or suspend the polyimide precursor (A) and the photopolymerization initiator (B) according to this embodiment. Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. Among these, from the viewpoint of low dielectric constant, it is preferable that at least one is selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide, with γ-butyrolactone and dimethyl sulfoxide being particularly preferred. These solvents may be used individually or as a mixture of two or more.

[0058] The above solvent can be used in an amount ranging from, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of (A) polyimide precursor, depending on the desired coating film thickness and viscosity of the photosensitive resin composition. If the solvent contains an alcohol without an olefinic double bond, the content of the alcohol without an olefinic double bond in the total solvent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. When the above content of the alcohol without an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of (A) polyimide precursor is improved.

[0059] [(D) Polymerization inhibitors] In this embodiment, it is preferable to add a polymerization inhibitor. By adding a polymerization inhibitor, the negative-type photosensitive resin composition can obtain good resolution regardless of the substrate material. Examples of polymerization inhibitors in this embodiment include compounds containing aromatic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds.

[0060] Compounds containing aromatic hydroxyl groups include 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and N,N'-hexane-1,6-diylbis[3-(3,5- [Di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3”,5,5',5”-Hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], Hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5- Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, catechol, tert-butyl-catechol, 4,4',4”-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, 3,9 Examples include -bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), phenolic resins, and cresol resins.

[0061] Examples of nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, Nt-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerium salt and N-nitrosophenylhydroxyamine aluminum salt, 2,4,6-Tris-t-butyl-nitrosobenzene, and N-nitrosodiphenylamine.

[0062] Examples of N-oxide compounds include phenyl-t-butylnitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline-N-oxide, 4-methylmorpholine-N-oxide, pyridine-N-oxide, 4-nitropyridine-N-oxide, 3-hydroxypyridine-N-oxide, picolinic acid-N-oxide, nicotinic acid-N-oxide, and isonicotinic acid-N-oxide.

[0063] Quinone compounds include p-benzoquinone, p-xyloquinone, p-toluquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amylbenzoquinone, 2-bromo-1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy -1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-H Examples include droxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, and 5,12-naphthacenquinone.

[0064] Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and piperidine 1-oxyl freeradiol. Examples include 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1-oxyl free radical compounds, and 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

[0065] Examples of phenothiazine compounds include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2-(trifluoromethyl)phenothiazine, and 2-methoxyphenothiazine.

[0066] From the viewpoint of development residue rate and resolution, compounds containing aromatic hydroxyl groups and nitroso compounds are preferred, and compounds containing aromatic hydroxyl groups are particularly preferred. As compounds containing aromatic hydroxyl groups, 4-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol are preferred, with 4-methoxyphenol being particularly preferred.

[0067] Furthermore, in the photosensitive resin composition of the present invention, the total content of (B) photopolymerization initiator and (D) polymerization inhibitor is preferably 0.1 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor component.

[0068] [(E) Other ingredients] The negative-type photosensitive resin composition of the present invention may further contain components other than those listed above (A) to (D). The negative-type photosensitive resin composition of the present invention is typically used as a liquid photosensitive resin composition obtained by dissolving each of the above components and any additional components as needed in a solvent (C) to form a varnish. For this reason, (E) other components can include, for example, resins other than the above (A) photosensitive polyimide precursor, sensitizers, crosslinking agents, monomers having photopolymerizable unsaturated bonds, adhesive aids, azole compounds, hindered phenol compounds, and the like. Examples of crosslinking agents include any compound having multiple functional groups within its molecule. Examples of functional groups include acrylic groups, methacrylic groups, epoxy groups, methylol groups, allyl groups, vinyl groups, maleimide groups, and the like.

[0069] The negative-type photosensitive resin composition according to this embodiment may further contain resin components other than the (A) polyimide precursor described above. Examples of resin components that can be included include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The amount of these resin components blended is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0070] The negative-type photosensitive resin composition according to this embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizers include Michlaz ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone,

[0071] 3,3'-Carbonyl-bis(7-diethylaminocoumarin), 3-Acetyl-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, Dimethylamino Examples include isoamyl benzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. These can be used individually or in combinations of, for example, 2 to 5 types.

[0072] When a negative-type photosensitive resin composition contains a sensitizer to improve light sensitivity, the amount of sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0073] The negative-type photosensitive resin composition of the present invention may optionally contain monomers having photopolymerizable unsaturated bonds to improve the resolution of the relief pattern. Preferred such monomers are (meth)acrylic compounds that undergo radical polymerization with a photopolymerization initiator. These include, but are not limited to, mono- or di(meth)acrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; Mono- or di(meth)acrylates of propylene glycol or polypropylene glycol; Glycerol mono, di, or tri(meth)acrylates; Cyclohexane di(meth)acrylate; Diacrylates and dimethacrylates of 1,4-butanediol, and di(meth)acrylates of 1,6-hexanediol;

[0074] Neopentyl glycol di(meth)acrylate; Mono- or di(meth)acrylate of bisphenol A; Benzene trimethacrylate; Isobornyl (meth)acrylate; Acrylamide and its derivatives; Methacrylamide and its derivatives; Trimethylolpropane tri(meth)acrylate; Glycerol di or tri(meth)acrylate; Pentaerythritol di, tri, or tetra(meth)acrylate; Furthermore, examples of compounds such as ethylene oxide or propylene oxide adducts of these compounds can be given.

[0075] In order to improve the resolution of the relief pattern formed from the negative-type photosensitive resin composition according to this embodiment, the amount of the above-mentioned photopolymerizable monomer having an unsaturated bond is preferably 0.01 to 50 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0076] To improve the adhesion between the film (photosensitive resin layer) formed from the negative-type photosensitive resin composition according to this embodiment and the substrate, adhesive aids may be optionally added to the photosensitive resin composition. Examples of adhesive aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidic acid, and benzophenone-3 Examples include silane coupling agents such as 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, and N-phenyl-3-aminopropyltrimethoxysilane, as well as aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0077] Of these adhesive aids, silane coupling agents are more preferable in terms of adhesive strength. When the photosensitive resin composition contains an adhesive aid, the amount blended is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0078] When the substrate to which the negative-type photosensitive resin composition according to this embodiment is applied is, for example, a substrate made of copper or a copper alloy, an azole compound can be optionally added to suppress discoloration of the copper surface. Examples of 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]-benz Examples include zotriazole, 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, 1-methyl-1H-tetrazol, etc. Particularly preferred are one or more selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used individually or as a mixture of two or more.

[0079] When the negative-type photosensitive resin composition according to this embodiment contains the above-mentioned azole compound, the amount blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of azole compound blended per 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, when a film (photosensitive resin layer) made of the negative-type photosensitive resin composition according to this embodiment is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed, while when it is 10 parts by mass or less, the excellent photosensitivity of the negative-type photosensitive resin composition is maintained.

[0080] To suppress discoloration of the copper surface, a hindered phenol compound may be optionally added in place of the azole compound, or together with the azole 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), and 4,4'-thiobis(3-methyl-6-t- Butylphenol), 4,4'-Butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-Hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-Thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],

[0081] 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), pentaerythrityltetrakis[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,

[0082] 1,3,5-Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-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,

[0083] Examples include, but are not limited to, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among 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.

[0084] The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the blending amount of the hindered phenol compound is 0.1 part by mass or more based on 100 parts by mass of the polyimide precursor (A), for example, when the negative 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. On the other hand, when it is 20 parts by mass or less, the excellent photosensitivity of the negative photosensitive resin composition is maintained.

[0085] For the negative photosensitive resin composition according to this embodiment, the weight loss rate when the cured film cured at 230°C for 2 hours is heated at 350°C is preferably 0.5 to 3.0%. The measurement of the weight loss rate was performed by the method described in the examples below. By setting the weight loss rate to 0.5% or more, the encapsulant deterioration test tends to be good. 0.6% or more is preferable, and 0.7% or more is more preferable. By setting the weight loss rate to 3.0% or less, the encapsulant adhesion tends to be good. 2.9% or less is preferable, and 2.8% or less is more preferable.

[0086] For the negative photosensitive resin composition according to this embodiment, in the weight loss component when the cured film cured at 230°C for 2 hours is heated at 350°C, the proportion derived from R1 and R2 in the general formula (A1) is preferably 60 to 80%. By setting it to 60% or more, the dielectric constant and dielectric tangent of the cured film tend to be good. 62% or more is more preferable, and 65% or more is particularly preferable. By setting it to 80% or less, the developability tends to be good. 78% or less is more preferable, and 75% or less is particularly preferable.

[0087] In this embodiment, a cured film obtained by curing a polyimide precursor represented by the following general formula (A1), wherein the weight loss rate of the cured film when heated at 350°C is 0.5 to 3.0%, and the proportion derived from R1 and R2 in the following general formula (A1) in the weight loss component is 60 to 80%, can be provided. [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] {(In the general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.)} This represents a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms at the same time.} A weight loss rate of 0.5% or more tends to result in better performance in the sealant degradation test. 0.6% or more is preferable, and 0.7% or more is more preferable. A weight reduction rate of 3.0% or less tends to result in good adhesion of the sealant. 2.9% or less is preferable, and 2.8% or less is more preferable.

[0088] It is preferable that the proportions derived from R1 and R2 in the above general formula (A1) are 60-80%. When it is 60% or more, the dielectric constant and dielectric loss tangent of the cured film tend to be good. 62% or more is more preferable, and 65% or more is particularly preferable. When it is 80% or less, the developability tends to be good. 78% or less is more preferable, and 75% or less is particularly preferable.

[0089] The cured film, in the IR spectrum of the cured film, shows (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500cm) -1 The absorption peak value in the vicinity is preferably between 0.3 and 0.54. Among these, from the viewpoint of exhibiting a low dielectric constant, a value of 0.54 or less is more preferable, and 0.5 or less is particularly preferable. Furthermore, from the viewpoint of developability, a value of 0.3 or higher is preferable, and 0.35 or higher is more preferable.

[0090] Furthermore, it is preferable that the cured film has a dielectric loss tangent of 0.001 to 0.009 at 10 GHz. This range tends to reduce signal delays when packaged in an AiP or similar device.

[0091] In this embodiment, a cured film can be provided which is obtained by curing a polyimide precursor containing the structure represented by the following general formula (A1), wherein the imide group concentration of the polyimide in the cured film is 12.0% to 25.0%, and the weight loss rate of the cured film when heated at 350°C is 0.5% to 3.0%. [ka] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are each independently hydrogen atoms, as shown in the general formula (R1): [ka] {In the general formula (R1), R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} This represents a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms at the same time.

[0092] Here, the imide group concentration refers to the proportion of imide groups per repeating unit of the polyimide cured film according to this embodiment. When the imide group concentration is 12% or higher, the adhesion between the mold resin and the cured relief pattern tends to be good. 12.5% ​​or higher is more preferable, and 13.5% or higher is particularly preferable. When the imide group concentration is 25.0% or lower, the dielectric loss tangent of the resulting polyimide cured film tends to be good. 24.0% or lower is more preferable, 23.0% or lower is even more preferable, and 21.0% or lower is particularly preferable.

[0093] Furthermore, a weight loss rate of 0.5% or more tends to result in better performance in the sealant degradation test. 0.6% or more is preferable, and 0.7% or more is more preferable. A weight reduction rate of 3.0% or less tends to result in good adhesion of the sealant. 2.9% or less is preferable, and 2.8% or less is more preferable.

[0094] The cured film, in the IR spectrum of the cured film, shows (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500cm) -1 The absorption peak value in the vicinity is preferably between 0.3 and 0.54. Among these, from the viewpoint of achieving a low dielectric loss tangent, a value of 0.54 or less is more preferable, and 0.5 or less is particularly preferable. Furthermore, from the viewpoint of developability, a value of 0.3 or more is preferable, and 0.35 or more is more preferable.

[0095] Furthermore, it is preferable that the cured film has a dielectric loss tangent of 0.001 to 0.009 at 10 GHz. This range tends to reduce signal delays when packaged in an AiP or similar device.

[0096] Preferably, the cured film contains 30% or less of solid components other than polyimide. Examples of solid components other than polyimide include crosslinkable monomers and polymerization components of 2-hydroxyethyl methacrylate (HEMA). This range makes it possible to achieve a low dielectric loss tangent. Furthermore, from the viewpoint of sealant adhesion, it is more preferable that the ratio of solid components other than polyimide be 27% or less.

[0097] Furthermore, it is preferable that the cured film contains 1000 ppm or less of compounds having hydroxyl groups and a molecular weight of 200 or less. Examples of compounds having hydroxyl groups and a molecular weight of 200 or less include monomers and polymerization components of HEMA. By keeping the concentration within this range, it is possible to reduce the polarity of the film and achieve a low dielectric loss tangent. Moreover, from the viewpoint of further reducing the dielectric loss tangent, it is even more preferable that the ratio of compounds having hydroxyl groups and a molecular weight of 200 or less be 500 ppm or less.

[0098] The manufacturing method of the cured film of this embodiment includes at least a coating step of forming a film of a composition containing a photosensitive polyimide precursor, and a curing step of polyimidizing the film containing the polyimide precursor. The curing step includes a heating step at 150 to 250 °C. The imide group concentration of the polyimide in the cured film is 12.0% to 25.0%. The weight loss rate of the cured film when heated at 350 °C is 0.5 to 3.0%. In the heat curing step, by heating at 150 to 250 °C and relatively low temperature, the warpage after heat curing can be reduced, and a highly reliable semiconductor device can be obtained.

[0099] In the manufacturing method of the cured film of this embodiment, it is preferable that the ratio of the solid components other than polyimide in the cured film is 30% or less.

[0100] In the manufacturing method of the cured film of this embodiment, it is preferable that the component derived from the photosensitive group of the polyimide precursor in the cured film is 1000 ppm or less. The component derived from the photosensitive group of the polyimide precursor is, for example, a compound having a hydroxyl group and a molecular weight of 200 or less.

[0101] <Method for Manufacturing Polyimide and Polyimide> The present invention also provides a method for manufacturing polyimide. The method for manufacturing polyimide in the present invention includes curing the above-mentioned negative photosensitive resin composition. The structure of the polyimide formed from the above negative photosensitive resin composition (polyimide precursor composition) is represented by the following general formula (2).

Chemical formula

[0102] <Method for manufacturing hardened relief patterns> The present invention also provides a method for manufacturing a cured relief pattern. The method for manufacturing a cured relief pattern in the present invention involves, for example, the following steps: (1) A coating step of applying the negative-type photosensitive resin composition of the present invention described above onto a substrate to form a photosensitive resin layer on the substrate, (2) An exposure step of exposing the photosensitive resin layer, (3) A developing step in which the photosensitive resin layer after exposure is developed to form a relief pattern, (4) A heating step in which a hardened relief pattern is formed by heat treatment of the relief pattern. The process is characterized by passing through the above-mentioned sequence. The following describes typical aspects of each process.

[0103] (1) Coating process In this process, the negative-type photosensitive resin composition of the present invention is applied to a substrate, and if necessary, then dried to form a photosensitive resin layer. The substrate may be a metal substrate made of, for example, silicon, aluminum, copper, copper alloy, etc. Resin substrates such as epoxy, polyimide, and polybenzoxazole; A substrate on which a metal circuit is formed on the resin substrate; A substrate in which multiple metals, or metals and resins, are laminated in multiple layers. You can use the following. As for the coating method, conventional methods used for coating photosensitive resin compositions, such as coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray coating with a spray coater, can be used.

[0104] If necessary, the photosensitive resin composition film can be dried. Drying methods include air drying, heating with an oven or hot plate, and vacuum drying. Furthermore, it is desirable to dry the coating film under conditions that prevent imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition. Specifically, when air drying or heating drying is performed, drying can be carried out at 20°C to 140°C for 1 minute to 1 hour. By doing so, a photosensitive resin layer can be formed on the substrate.

[0105] (2) Exposure process In this step, the photosensitive resin layer formed above is exposed to light. Exposure devices such as contact aligners, mirror projection machines, and steppers are used. Exposure can be performed via a patterned photomask or reticle, or directly. The light source used for exposure is, for example, an ultraviolet light source.

[0106] After exposure, post-exposure baking (PEB) and / or pre-development baking may be performed as needed, using any combination of temperature and time, for purposes such as improving photosensitivity. The preferred baking conditions are a temperature of 40 to 120°C and a time of 10 to 240 seconds, but are not limited to this range as long as they do not impair the properties of the negative-type photosensitive resin composition of this embodiment.

[0107] (3)Developing process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. Conventional photoresist development methods can be selected and used for developing the photosensitive resin layer after exposure (irradiation). Examples include rotary spraying, paddle application, and immersion with ultrasonic treatment. Furthermore, after development, post-development baking may be performed using any combination of temperature and time as needed, for purposes such as adjusting the shape of the relief pattern. The temperature for post-development baking can be, for example, 80-130°C, and the time can be, for example, 0.5-10 minutes.

[0108] The developer used for developing is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Preferred good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone, while preferred poor solvents include 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 of each solvent, for example, can be used in combination.

[0109] (4)Heating 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 to convert it into a cured relief pattern made of polyimide. Various methods can be used for heat curing, including using a hot plate, an oven, or a heating oven with a set temperature program. Heating can be carried out, for example, at temperatures between 160°C and 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. In this manner, a hardened relief pattern can be manufactured.

[0110] <Semiconductor device> The present invention also provides a semiconductor device having a cured relief pattern obtained by the method for manufacturing the cured relief pattern of the present invention described above. The semiconductor device described above may be, for example, a semiconductor device having a substrate which is a semiconductor element and a cured relief pattern formed on the substrate by the cured relief pattern manufacturing method described above. The semiconductor device described above can be manufactured, for example, by using a semiconductor element as a substrate and including the method for manufacturing the cured relief pattern 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 above cured relief pattern manufacturing method as, for example, a surface protective film, an interlayer insulating film, an insulating film for redistribution, 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.

[0111] 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 in multilayer circuits, cover coatings for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films.

[0112] ≪Modes for Carrying Out the Second Invention≫

[0113] The following describes in detail embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its essence. Throughout this specification, structures represented by the same symbols in a general formula may be identical or different from each other if multiple such structures exist in a molecule.

[0114] <Negative-type photosensitive resin composition> The negative-type photosensitive resin composition according to this embodiment consists of the following components: (A) Polyimide precursor; (B) Photopolymerization initiator; (C) Silane coupling agents having a specific structure; and (D) Certain organic solvents; Includes.

[0115] From the viewpoint of obtaining high resolution, the negative-type photosensitive resin composition preferably contains 100 parts by mass of (A) a polyimide precursor, 0.1 to 20 parts by mass of (B) a photopolymerization initiator based on 100 parts by mass of (A) the polyimide precursor, and 0.1 to 20 parts by mass of (C) a silane coupling agent having a specific structure based on 100 parts by mass of (A) the polyimide precursor.

[0116] (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 given by the following general formula (2): [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.} It is preferable that the polyamide has structural units represented by .

[0117] At least one of R1 and R2 is preferably the following general formula (3): [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.} It is a monovalent organic group represented by .

[0118] In general formula (2), n1 is not limited to any integer between 2 and 150, but from the viewpoint of the 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.

[0119] In general formula (2), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group or alicyclic aliphatic group in which the -COOR1 and -COOR2 groups and the -CONH- group are in the ortho position relative to each other. Specifically, the tetravalent organic group represented by X1 is an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20): [ka] Groups having the structure represented by {wherein R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; l is an integer selected from 0 to 2; m is an integer selected from 0 to 3; and n is an integer selected from 0 to 4.} are examples of groups, but are not limited to these. Furthermore, the structure of X1 may be one type or a combination of two or more types. An X1 group having the structure represented by the above formula (20) is preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0120] As for the X1 group, among the structures represented by the above formula (20), the following formulas (20A), (20B), or (20C): [ka] [ka] [ka] The structure represented by the following formulas (20a), (20b), or (20c) is more preferable from the viewpoint of chemical resistance, resolution, and void suppression after high-temperature storage tests: [ka] [ka] [ka] The structure represented by is particularly preferred.

[0121] In the above general formula (2), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, for example, the following formula (21): [ka] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} Examples of structures represented by the above formula (21) are, but are not limited to, those shown. Furthermore, the structure of Y1 may be one type or a combination of two or more types. A Y1 group having the structure represented by the above formula (21) is preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0122] As for the Y1 group, among the structures represented by the above formula (21), the following formulas (21A), (21B), or (21C): [ka] [ka] [ka] The structure represented by the following formula (21b) or (21c) is preferred from the viewpoint of chemical resistance, resolution, and void suppression after high-temperature storage tests: [ka] [ka] The structure represented by is particularly preferred.

[0123] In the above general formula (3), 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.

[0124] In one embodiment, (A) the polyimide precursor is given by the following general formula (4): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150.} It is preferable that the polyimide precursor has a structural unit represented by . In general formula (4), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by general formula (3). (A) The polyimide precursor containing the polyimide precursor represented by general formula (4) particularly enhances the resolution effect.

[0125] In one embodiment, (A) the polyimide precursor is given by the following general formula (5): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150.} It is preferable that the polyimide precursor has a structural unit represented by . In general formula (5), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by general formula (3). (A) The resolution effect is further enhanced, in particular, by including the polyimide precursor represented by general formula (5) in addition to the polyimide precursor represented by general formula (4).

[0126] Among these, (A) polyimide precursor is particularly preferable from the viewpoint of chemical resistance, resolution, and void suppression after high-temperature storage tests if it simultaneously contains the structural units represented by the above general formulas (4) and (5), or is a copolymer of the structural units represented by the above general formulas (4) and (5). When (A) polyimide precursor is a copolymer of structural units represented by the general formulas (4) and (5), R1, R2, and n1 in one formula may be the same as, or different from, R1, R2, and n1 in the other formula, respectively.

[0127] In one embodiment, (A) the polyimide precursor is given by the following general formula (6): [ka] {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a monovalent organic group, and n1 is an integer between 2 and 150.} It is preferable that the polyimide precursor has a structural unit represented by . In general formula (6), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by general formula (3). (A) The effect of chemical resistance is particularly enhanced when the polyimide precursor contains a polyimide precursor represented by general formula (6).

[0128] (A) Method for preparing polyimide precursors (A) The polyimide precursor is first obtained by reacting a tetracarboxylic dianhydride containing the tetravalent organic group X1 in the general formula (2) with photopolymerizable alcohols having an unsaturated double bond and optionally alcohols without an unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also called an acid / ester), and then by amide polycondensation of this with diamines containing the divalent organic group Y1 in the general formula (2).

[0129] (Preparation of acid / ester compounds) In this embodiment, the tetracarboxylic dianhydride containing the tetravalent organic group X1, which is suitably used to prepare (A) the polyimide precursor, includes, for example, tetracarboxylic dianhydrides having the structure shown in the general formula (20) above, as well as pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, and diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride. Examples of suitable materials include water, 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 preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. These can be used individually or in combination of two or more.

[0130] In this embodiment, suitable photopolymerizable alcohols having unsaturated double bonds for preparing (A) polyimide precursors include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy Examples include -3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl 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.

[0131] 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.

[0132] 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.

[0133] 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, and then mixing them, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0134] (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.

[0135] 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, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 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)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)hex Safluoropropane, 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-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,Examples include, but are not limited to, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyltoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0136] 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, 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.

[0137] 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 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.

[0138] (B) Photopolymerization initiator The (B) photopolymerization initiator used in this embodiment will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, and includes 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-methoxy Preferred photopolymerization initiators include, but are not limited to, oximes such as carbonyl oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 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 from the viewpoint of photosensitivity.

[0139] The amount of (B) photopolymerization initiator in the negative-type photosensitive resin composition 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.

[0140] (C) Silane coupling agents having a specific structure (C) A silane coupling agent having a specific structure used in this embodiment will be described. The silane coupling agent having a specific structure (C) according to this embodiment has a structure represented by the following general formula (1). [ka] {In the formula, a is an integer from 1 to 3, n is an integer from 1 to 6, and R 21 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 22 R is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R 20 This is at least one substituent selected from the group consisting of an epoxy group, a phenylamino group, and a ureid group. In general formula (1), a is not limited to any integer between 1 and 3, but from the viewpoint of adhesion to the metal redistribution layer, 2 or 3 is preferred, and 3 is more preferred. n is not limited to any integer between 1 and 6, but from the viewpoint of adhesion to the metal redistribution layer, it is preferably between 1 and 4. From the viewpoint of developability, it is preferably between 2 and 5. R 21 The alkyl group is not limited to those having 1 to 4 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. R 22 This is not limited to a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include R 21 Similar alkyl groups can be given as examples. R 20 The substituent is not limited to any substituent containing an epoxy group, a phenylamino group, a ureido group, or an isocyanate group. Among these, from the viewpoint of developability and adhesion of the metal redistribution layer, it is preferable that it be at least one selected from the group consisting of substituents containing a phenylamino group and substituents containing a ureido group, and more preferably substituents containing a phenylamino group. Examples of silane coupling agents containing epoxy groups include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. An example of a silane coupling agent containing a phenylamino group is N-phenyl-3-aminopropyltrimethoxysilane. An example of a silane coupling agent containing a ureido group is 3-ureidopropyltrialkoxysilane. An example of a silane coupling agent containing an isocyanate group is 3-isocyanatetopropyltriethoxysilane.

[0141] (D) Organic solvents having a specific structure The organic solvent used in this embodiment is not limited as long as it contains at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, and ε-caprolactone. The inclusion of the above organic solvent allows for sufficient adhesion to the sealing material. Among these, (A) from the viewpoint of solubility of the polyimide precursor, γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, and ε-caprolactone are preferred, and from the viewpoint of suppressing copper surface voids, it is more preferable to include at least two organic solvents selected from the above group.

[0142] The reason why the organic solvent having a specific structure according to this embodiment exhibits good adhesion to the sealing material is not clear, but the inventors have the following hypothesis. Conventionally, organic solvents used to dissolve photosensitive resin compositions containing polyimide precursors have been amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. While these solvents have extremely high solubility for polyimide precursors, when the required heat curing temperature is low (e.g., below 200°C), they tend to remain in the film in large quantities due to their high affinity for the resulting polyimide. This can lead to a decrease in performance due to interactions with silane coupling agents having the specific structure described above (C). On the other hand, by including the above-mentioned solvents, even at low heat curing temperatures, the amount of solvent remaining in the film after heat curing can be sufficiently reduced, resulting in good adhesion to the encapsulant.

[0143] In the negative-type photosensitive resin composition of this embodiment, the amount of organic 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.

[0144] (E) Thermobase generator The negative-type photosensitive resin composition of this embodiment may further contain components other than those described above (A) to (D). In particular, it is more preferable to include (E) a thermal base generator in order to accommodate lower heat curing temperatures. A base-generating agent is a compound that generates a base when heated. Including a thermal base-generating agent can further promote the imidization of the photosensitive resin composition.

[0145] While there is no specific type of thermobase generator, examples include amine compounds protected by a tert-butoxycarbonyl group and the thermobase generator disclosed in International Publication No. 2017 / 038598. However, these are not limited to these, and other known thermobase generators can be used.

[0146] Examples of amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropyl) Ropyramino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrroridinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown Examples include, but are not limited to, 5-ethers, diethylene glycol bis(3-aminopropyl) ethers, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a tert-butoxycarbonyl group.

[0147] (E) The compounding amount of the thermal base generator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. From the viewpoint of the imidization promotion effect, the above compounding amount is 0.1 part by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition, it is preferably 20 parts by mass or less.

[0148] The negative photosensitive resin composition of this embodiment may further contain components other than the above components (A) to (E). Examples of the components other than the components (A) to (E) include, but are not limited to, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, thermal polymerization inhibitors, and the like.

[0149] <Nitrogen-containing heterocyclic compound> When forming a cured film on a substrate made of copper or a copper alloy using the negative photosensitive resin composition of this embodiment, in order to suppress discoloration on copper, the negative photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound. Specifically, examples include azole compounds and purine derivatives.

[0150] 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]-benzo Examples include riazole, 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.

[0151] Particularly preferred are toltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used individually or as a mixture of two or more.

[0152] Specific examples of 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, 8- Examples include minoadenine, 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-azaxanthin, 8-azahypoxanthin, and their derivatives.

[0153] When the negative-type photosensitive resin composition contains the above-mentioned azole compound or purine derivative, the amount blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of azole compound blended per 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, when the negative-type photosensitive resin composition of this embodiment is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed, while when it is 20 parts by mass or less, the photosensitivity is excellent.

[0154] <Hindered phenol compounds> Furthermore, 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-Triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-Triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl Triz(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazin-2,4,6-(1H,3H,5H)-trione, Triz(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazin-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-tri Examples include, but are not limited to, azine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among 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.

[0155] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the (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 the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the negative-type photosensitive resin composition of this embodiment 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.

[0156] <Organo-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.

[0157] Examples of usable 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).

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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, and 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.

[0162] 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 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.

[0163] <Sensitizer> The negative-type photosensitive resin composition of this embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of such 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-dimethylaminocinnamyridene ind Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone Examples include ethyl-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-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used individually or in combinations of, for example, 2 to 5 types.

[0164] When a negative-type photosensitive resin composition contains a sensitizer to improve light sensitivity, the amount of sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0165] <Photopolymerizable unsaturated monomers> The negative-type photosensitive resin composition may optionally contain monomers having photopolymerizable unsaturated bonds 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.

[0166] When the photosensitive resin composition contains the above-mentioned photopolymerizable unsaturated monomer for improving the resolution of the relief pattern, the amount of the photopolymerizable unsaturated monomer is preferably 1 to 50 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0167] <Thermal polymerization inhibitor> Furthermore, 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.

[0168] <Method for manufacturing a hardened relief pattern and semiconductor device> Furthermore, the present invention provides a method for manufacturing a cured relief pattern, comprising the steps of: (1) 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) exposing the photosensitive resin layer to light; (3) developing the photosensitive resin layer after exposure to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

[0169] (1) Photosensitive resin layer formation process In this process, the negative-type photosensitive resin composition of the present invention is applied to a substrate, and if necessary, it is then 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, or spray application using a spray coater.

[0170] If necessary, the coating containing the negative-type 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 under conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a photosensitive resin layer (negative-type photosensitive resin layer) can be formed on the substrate.

[0171] (2) Exposure process In this process, the negative-type photosensitive resin layer formed above is exposed to ultraviolet light or the like, either through a patterned photomask or reticle, or directly, using an exposure device such as a contact aligner, mirror projection, or stepper.

[0172] Subsequently, if necessary, post-exposure baking (PEB) and / or pre-development baking may be performed using any combination of temperature and time to improve light sensitivity, etc. While the baking conditions are preferably within a range of 40°C to 120°C and 10 to 240 seconds, they are not limited to this range as long as they do not impair the properties of the negative-type photosensitive resin composition of the present invention.

[0173] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. 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.

[0174] 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.

[0175] (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.

[0176] <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 (8). [ka] {where, X 1 and Y 1 These are the same as X1 and Y1 in general formula (2), and m is a positive integer. The preferred X1 and Y1 in general formula (2) are also preferred in the polyimide of general formula (8) for the same reasons. The number of repeating units m in general formula (8) can be any positive integer and is not particularly limited, but may be an integer between 2 and 150, or an integer between 3 and 140.

[0177] Furthermore, a method for producing polyimide, which includes a step of converting the negative-type photosensitive resin composition described above into polyimide, is also one embodiment of the present invention.

[0178] <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.

[0179] <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 thin-film transistor (TFT) liquid crystal display elements and color filter elements, a projection for a multi-domain vertical alignment (MVA) type liquid crystal display device, and a partition for the cathode of an organic electroluminescent (EL) element.

[0180] 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]

[0181] <<Example of the First Invention>> The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The physical properties of the photosensitive resin compositions in the examples, comparative examples, and manufacturing examples were measured and evaluated according to the following methods.

[0182] (1) Weight average molecular weight The weight-average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (on a standard polystyrene basis). The columns used for the measurement were Showa Denko Corporation's Shodex 805M / 806M in series. The standard monodisperse polystyrene was Showa Denko Corporation's Shodex STANDARD SM-105, the developing solvent was N-methyl-2-pyrrolidone, and the detector was Showa Denko Corporation's Shodex RI-930.

[0183] (2) Focus margin evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm) was sputtered with 200nm thick Ti and then 400nm thick Cu in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Cu wafer substrate. A negative-type photosensitive resin composition was spin-coated onto the above-mentioned sputtered Cu wafer substrate using a spin-coating apparatus (D-spin60A model, manufactured by SOKUDO Corporation), and then heated and dried at 110°C for 180 seconds to produce a spin-coated film with a thickness of 10 μm ± 0.2 μm.

[0184] Exposure was performed on this spin-coated film using a PrismaGHI S / N5503 (Ultratech) 1:1 projection lithography system with a test pattern reticle having a circular pattern with a mask size of 15 μm in diameter. During this process, for each exposure dose, the focus was moved 2 μm increments, relative to the surface of the spin-coated film, towards the bottom of the film. Next, the coating film formed on the sputtered Cu wafer was spray-developed using cyclopentanone in a developer (D-SPIN636 model, manufactured by Dainippon Screen Co., Ltd.), and then rinsed with propylene glycol methyl ether acetate to obtain a circular recessed relief pattern of polyamic acid ester. The development time for spray development was defined as 1.4 times the minimum time required for the unexposed resin composition to develop in the 10 μm spin-coated film described above.

[0185] For the circular recessed relief patterns with a mask size of 15 μm obtained above, the ability to open was determined by whether the pattern met both of the following criteria (I) and (II). The thickness of the focus margin that gave the pattern an acceptable result is recorded in the results. (I) The area of ​​the pattern opening is at least half the area of ​​the corresponding pattern mask opening. (II) The pattern cross section is not tapered, and there is no undercutting, swelling, or bridging.

[0186] (3) Degradation test of sealing material As the epoxy encapsulant, we prepared the R4000 series manufactured by Nagase Chemtex Co., Ltd. Next, the encapsulant was spin-coated onto an aluminum sputtered silicon wafer to a thickness of approximately 150 μm, and then heat-cured at 130°C to cure the epoxy encapsulant. On the above-mentioned epoxy cured film, the negative-type photosensitive resin compositions prepared in each example and comparative example were applied to a final film thickness of 10 μm. The applied photosensitive resin composition film was subjected to a 300 mJ / cm² test. 2 The entire surface was exposed under the following exposure conditions. Subsequently, it was heat-cured at 230°C for 2 hours to produce the first layer of cured film with a thickness of 10 μm.

[0187] On top of the first cured layer described above, the negative-type 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 μm.

[0188] After the second layer of cured film had formed, the test specimens were cut crosswise using a FIB device (JEOL Ltd., JIB-4000), and the degree of degradation was evaluated by checking for the presence or absence of voids in the epoxy portion. Specimens without voids were marked with ○, and specimens with even one void were marked with ×.

[0189] (4) Adhesion test with sealing material In the sealing material degradation test, pins were inserted into the prepared samples, and adhesion tests were performed using a take-up test machine (Quad Group, Sebastian 5). Specifically, the adhesion between the epoxy sealing material and the cured relief patterns prepared from the photosensitive resin compositions in each example and comparative example was tested. Rating: Adhesion strength 70 MPa or higher... Excellent adhesion. 50 MPa or more - less than 70 MPa... Adhesion strength: Good 30 MPa or more - less than 50 MPa... Adhesion strength △ Less than 30 MPa... poor adhesion

[0190] (5) Measurement of dielectric constant and dielectric loss tangent A 100nm thick layer of aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm) using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. A negative-type photosensitive resin composition was spin-coated onto the above-mentioned sputtered Al wafer substrate using a spin-coating apparatus (D-spin60A, manufactured by SOKUDO Corporation), and then heated and dried at 110°C for 180 seconds to produce a spin-coated film with a thickness of 10 μm ± 0.2 μm. Subsequently, exposure at 600 mJ / cm² was applied using an aligner (PLA-501F, manufactured by Canon Corporation). 2The entire surface was exposed using the GHI line, and a cured film was prepared by heat curing at 230°C for 2 hours under a nitrogen atmosphere using a vertical curing furnace (Koyo Lindbergh, model VF-2000B). This cured film was cut into 80mm x 60mm strips using a dicing saw (Disco, model DAD-2H / 6T), and peeled off from the silicon wafer by immersion in a 10% hydrochloric acid aqueous solution to obtain film samples.

[0191] The relative permittivity and dielectric loss tangent of film samples were calculated at 10 GHz using the resonator perturbation method. Details of the measurement method are as follows. (Measurement method) Perturbation-type split-cylinder resonator method (Device configuration) Network analyzer: PNA Network analyzer E5224B (manufactured by Agilent Technologies) Split-cylinder resonator: CR-710 (manufactured by Kanto Electronics Applied Development Co., Ltd.) Measurement frequency: about 10GHz

[0192] (6) IR measurement IR measurement was performed on the film obtained in (5) above using the ATR method with a Scientific Nicolet iN10 at 700-4000 cm². -1 The range was measured with 50 scans. 1380cm -1 Absorption peak values ​​in the vicinity, and at 1500 cm -1 By determining the absorption peak values ​​in the vicinity, (1380cm) -1 (Absorption peak value in the vicinity) / (1500cm) -1 The value of the absorption peak in the vicinity was calculated. The peak values ​​for each are 1380 cm. -1 , 1500cm -1 ±10cm -1 This was considered the largest peak.

[0193] (7) Weight loss rate measurement On a 6-inch silicon wafer, a photosensitive resin composition was spin-coated so that the film thickness after curing would be about 10 μm. After pre-baking on a hot plate at 110 °C for 180 seconds, it was heated at 230 °C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured polyimide coating film. The film thickness was measured using a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating film was scraped off, and when the temperature was raised from room temperature at 10 °C / min using a thermogravimetric measuring device (TGA-50, manufactured by Shimadzu Corporation), the weight of the film when it reached 230 °C was W 230 , and the weight of the film when it reached 350 °C was W 350 . The weight loss rate is determined by the following formula. Weight loss rate (%) = (W 230 - W 350 ) × 100 / W 230

[0194] (8) Calculation of the proportion derived from R1 and R2 in the weight loss component On a 6-inch silicon wafer, a photosensitive resin composition was spin-coated so that the film thickness after curing would be about 10 μm. After pre-baking on a hot plate at 110 °C for 180 seconds, it was heated at 230 °C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured polyimide coating film. The obtained polyimide coating film was taken out in strip form and subjected to thermal desorption GC / MS measurement. The sum of the areas of all peaks excluding CO2 and H2O in the thermal desorption GC / MS chromatogram was taken as 100%, and the proportion of the peak areas derived from R1 and R2 was calculated. The details of the measurement method are as follows.

[0195] (Pyrolysis) Measuring device: FRONTIER LAB PY2020iD (manufactured by Frontier Lab Co., Ltd.) Thermal desorption conditions: 350 °C × 30 minutes

[0196] (GC / MS) Measuring device: Agilent6890 / JEOL AM-SUN Column: DB-1 (0.25 mm i.d. × 30 m) Column temperature: 300°C x 12 minutes (heating rate: 20°C / min) Column flow rate: 1.0 mL / min Inlet temperature: 300℃ Interface temperature: 300℃ Ionization method: Electron ionization method Sample amount: Approximately 0.1 mg

[0197] (9) Calculation of radical generation amount of initiator after exposure The initiator was dissolved in DMSO solvent to a concentration of 100 μM, and the spin trapping agent, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), was dissolved to a concentration of 100 mM. 50 μl of these solutions were placed in a 2 mmΦ quartz sample tube, and immediately after UV irradiation, ESR measurements were performed under the following conditions. The UV lamp was irradiated using the filter shown below. Details are provided below.

[0198] (ESR measurement conditions) Equipment: Bruker E500 Microwave frequency: 9.87 GHz (X-band) Microwave power: 10.0mW Center magnetic field: 3517G Sweep magnetic field range: 120G Modulation frequency: 100kHz Modulated magnetic field amplitude: 1.0G Measurement temperature: 25℃ Sweep time: 30s Total number of times: 4

[0199] (UV exposure conditions) Equipment: Hamamatsu Photonics L9566-01A Specification filter: A9616-05 Irradiation time: 1s Output irradiation intensity: 40% Irradiation distance: 24mm Irradiation area: 0.4cm 2

[0200] <Manufacturing Example 1> ((A) Synthesis of Polyimide Precursor (Polymer A-1)) 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2-liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then left to stand for another 16 hours.

[0201] 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 with stirring. Subsequently, a suspension of 175.9 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (BAPP) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, after which 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0202] The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain powdered polymer A-1. The weight-average molecular weight (Mw) of polymer A-1 was measured to be 22,000, and the imide group concentration was 19.4%.

[0203] <Manufacturing Example 2> (Synthesis of polyimide precursor (polymer A-2)) Polymer A-2 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 169.9 g of bis{4-(4-aminophenoxy)phenyl}ketone was used instead of 175.9 g of BAPP in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-2 was measured to be 21,000, and the imide group concentration was 19.9%.

[0204] <Manufacturing Example 3> (Synthesis of Polyimide Precursor (Polymer A-3)) Polymer A-3 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used instead of 155.1 g of ODPA in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-3 was measured to be 26,000, and the imide group concentration was 15.0%.

[0205] <Manufacturing Example 4> (Synthesis of Polyimide Precursor (Polymer A-4)) Polymer A-4 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that in Production Example 2 described above, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 169.9 g of bis{4-(4-aminophenoxy)phenyl}ketone was used instead of 175.9 g of BAPP. The weight-average molecular weight (Mw) of polymer A-4 was measured to be 25,000, and the imide group concentration was 15.3%.

[0206] <Manufacturing Example 5> (Synthesis of Polyimide Precursor (Polymer A-5)) Polymer A-5 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that ODPA 77.6 g and 4,4'-(4,4'-isopropylidene diphenoxy) acid dianhydride 130.1 g were used instead of ODPA 155.1 g in Production Example 1. The weight-average molecular weight (Mw) of polymer A-5 was measured to be 24,000, and the imide group concentration was 17.0%.

[0207] <Manufacturing Example 6> (Synthesis of Polyimide Precursor (Polymer A-6)) Polymer A-6 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 73.6 g of BPDA and 130.1 g of 4,4'-(4,4'-isopropylidene diphenoxy) acid dianhydride were used instead of 155.1 g of ODPA in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-6 was measured to be 24,000, and the imide group concentration was 17.1%.

[0208] <Manufacturing Example 7> A-7 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 148.43 g of hydroxypropyl methacrylate was used instead of 134.0 g of HEMA in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-7 was measured to be 24,000, and the imide group concentration was 19.4%.

[0209] <Manufacturing Example 8> A-7 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 162.86 g of hydroxybutyl methacrylate was used instead of 134.0 g of HEMA. The weight-average molecular weight (Mw) of polymer A-8 was measured to be 26,000, and the imide group concentration was 19.4%.

[0210] <Manufacturing Example 9> A-9 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 187.92 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane was used instead of 175.9 g of BAPP in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-9 was measured to be 22,000, and the imide group concentration was 18.7%.

[0211] <Manufacturing Example 10> A-10 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 185.32 g of bis{4-(4-aminophenoxy)phenyl}sulfone was used instead of 175.9 g of BAPP in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-10 was measured to be 23,000, and the imide group concentration was 18.9%.

[0212] <Manufacturing Example 11> A-11 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane 222.15 g was used instead of 175.9 g of BAPP in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-11 was measured to be 23,000, and the imide group concentration was 16.9%.

[0213] <Manufacturing Example 12> A-12 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used instead of 155.1 g of ODPA, and 143.29 g of 1,4-bis(4-aminophenoxy)-2,3,5-trimethylbenzene was used instead of 175.9 g of BAPP. The weight-average molecular weight (Mw) of polymer A-12 was measured to be 22,000, and the imide group concentration was 16.4%.

[0214] <Manufacturing Example 13> A-13 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 173.34 g of 1,4-bis(4-aminophenoxy)-2,5-di-t-butylbenzene was used instead of 175.9 g of BAPP. The weight-average molecular weight (Mw) of polymer A-13 was measured to be 24,000, and the imide group concentration was 15.1%.

[0215] <Manufacturing Example 14> A-14 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 268.26 g of decanediol bis(trimellitic acid monoester anhydride) was used instead of 155.1 g of ODPA in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-14 was measured to be 22,000, and the imide group concentration was 14.8%.

[0216] <Manufacturing Example 15> (Synthesis of Polyimide Precursor (Polymer A-15)) Polymer A-15 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 239.2 g of 4,4'-bis(3,4-dicarboxyphenoxy)biphenylic acid dianhydride was used instead of 155.1 g of ODPA in Production Example 1 above. The weight-average molecular weight (Mw) of polymer A-15 was measured to be 27,000, and the imide group concentration was 15.8%.

[0217] <Manufacturing Example 16> (Synthesis of Polyimide Precursor (Polymer A-16)) Polymer A-16 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that BPDA 147.1g was used instead of ODPA 155.1g in Production Example 1. The weight-average molecular weight (Mw) of polymer A-16 was measured to be 23,000, and the imide group concentration was 19.9%.

[0218] <Manufacturing Example 17> (Synthesis of Polyimide Precursor (Polymer A-17)) Polymer A-17 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that BAPP 87.8g and BAPB 78.8g were used instead of BAPP 175.9g in Production Example 1. The weight-average molecular weight (Mw) of polymer A-17 was measured to be 24,000, and the imide group concentration was 20.0%.

[0219] <Manufacturing Example 18> (Synthesis of Polyimide Precursor (Polymer A-18)) Polymer A-18 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that BPDA 147.1g was used instead of ODPA 155.1g and 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane 187.92g was used instead of BAPP 175.9g. The weight-average molecular weight (Mw) of polymer A-18 was measured to be 25,000, and the imide group concentration was 19.1%.

[0220] <Manufacturing Example 19> A-19 was obtained by carrying out the reaction in the same manner as described in Production Example 1, except that 85.8 g of diaminodiphenyl ether was used instead of 175.9 g of BAPP in Production Example 1. The weight-average molecular weight (Mw) was measured to be 22,000, and the imide group concentration was 27.4%.

[0221] Photopolymerization initiator B1: 3-Cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]propanone-1-(O-acetyloxime) (Trade name: PBG-304, manufactured by Changzhou Strong Electronics Co., Ltd.) The amount of radicals generated was 27.9 μM. The amount of radicals generated by the photopolymerization initiator B2: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (trade name: PBG-305, manufactured by Changzhou Strong Electronics Co., Ltd.) was 8.0 μM. The radical generation amount of photopolymerization initiator B3: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyloxime) (trade name: PBG-3057, manufactured by Changzhou Strong Electronics Co., Ltd.) was 10.6 μM. Photopolymerization initiator B4: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime. The amount of radical generated was 0.8 μM. Solvent C1: γ-butyrolactone Solvent C2: Dimethyl sulfoxide (DMSO) Solvent C3: N-methyl-2-pyrrolidone Other ingredients M4G: Tetraethylene glycol dimethacrylate

[0222] <Example 1> A photosensitive resin composition solution was prepared by dissolving 100g of polymer A-1 as component (A) and a mixed solvent (weight ratio 75:25) consisting of photopolymerization initiator B1 (2g), γ-butyrolactone, and DMSO as component (B), and adjusting the amount of solvent so that the viscosity was approximately 35 poise. This composition was evaluated using the method described above. The evaluation results are shown in Table 2.

[0223] <Examples 2-28, Comparative Example 2> The evaluation was carried out in the same manner as in Example 1, except that the resin composition solution was prepared in the proportions shown in Table 1. The evaluation results are shown in Table 2.

[0224] [Table 1]

[0225] [Table 2]

[0226] As is clear from Table 2, the examples exhibited a large focus margin, good adhesion to the encapsulating material (molding resin), and a low dielectric constant, but the comparative examples did not yield satisfactory results.

[0227] An integrated antenna module was created by combining a fan-out type wafer-level chip-size package semiconductor device and an antenna using the photosensitive resin compositions prepared in the Examples and Comparative Examples. The photosensitive resin compositions prepared in the Examples and Comparative Examples were used as interlayer insulating films of the semiconductor device. In addition, the photosensitive resin compositions prepared in the Examples and Comparative Examples were also used as insulating materials between the antenna and the ground (reference potential). Since the thickness of this insulating material affects the radiance of the antenna, the thickness was set to obtain the maximum radiation efficiency.

[0228] Furthermore, the integrated antenna module was designed to operate at 300GHz. The reflection characteristics (electrical characteristics) were evaluated, and those with a deviation of less than 5 GHz from the antenna alone at 300 GHz were marked with ○, those between 5 GHz and 10 GHz were marked with △, and those above 10 GHz were marked with ×. Here, reflection characteristics represent the ratio of the amount of power reflected by the antenna and returned to the input port to the input power input to the antenna. As a result, all of Examples 1 to 29 received a "○", Comparative Example 1 received a "△", and Comparative Example 2 received a "×".

[0229] While embodiments of the present invention have been described above, the present invention is not limited thereto and can be modified as appropriate without departing from the spirit of the invention.

[0230] ≪Example of the Second Invention≫

[0231] The present invention will be specifically described below with reference to examples, but the present invention 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.

[0232] <Measurement and Evaluation Methods> (1) Weight average molecular weight The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (on a standard polystyrene basis) under the following conditions. 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.

[0233] (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. 2 The coating was irradiated with energy. Next, the coating was spray-developed using cyclopentanone as the developer with a coater developer (D-Spin 60A, manufactured by SOKUDO), and then rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. A wafer on which the relief pattern was formed on Cu was heated in a nitrogen atmosphere at the curing temperature shown in Table 3 for 2 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), thereby obtaining a cured relief pattern on Cu consisting of resin with a thickness of approximately 4 to 5 μm.

[0234] (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 rated "Excellent," those between 10 μm and 14 μm were rated "Good," those between 14 μm and 18 μm were rated "Acceptable," and those with a resolution of 18 μm or more were rated "Unacceptable."

[0235] (4) High-temperature storage test of hardened relief pattern on Cu and subsequent evaluation of 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 are 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

[0236] 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-Image-kun, manufactured by Asahi Kasei Corporation). When the total area of ​​voids in the photosensitive resin composition described in Comparative Example 1 was evaluated, the total area ratio of voids was judged as "Excellent" if it was less than 50%, "Good" if it was between 50% and 75%, "Acceptable" if it was between 75% and 100%, and "Unacceptable" if it was 100% or more.

[0237] (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 and 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, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution, such as cracks, and / or the rate of change in film thickness after chemical treatment. As an evaluation criterion, no damage such as cracks occurred and the rate of change in film thickness was 10% or less relative to the film thickness before chemical immersion was classified as "Excellent," 10-15% as "Good," 15-20% as "Acceptable," and cracks occurred or the rate of change in film thickness exceeded 20% as "Unacceptable."

[0238] (6) Adhesion test with sealing material We prepared the R4000 series from Nagase Chemtex Co., Ltd. as an epoxy-based sealant. Next, 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. The photosensitive resin compositions prepared in the examples and comparative examples were then applied onto the epoxy-cured film to a final film thickness of 10 microns. The applied photosensitive resin composition was subjected to a 500 mJ / cm² test. 2 After exposing the entire surface under the specified exposure conditions, the first layer of cured film with a thickness of 10 microns was fabricated by heat curing at 180°C for 2 hours. The photosensitive resin composition used to form the first layer of cured film was applied to the first layer of cured film, and after exposing the entire surface under the same conditions as when the first layer of cured film was prepared, it was heat-cured to produce a second layer of cured film with a thickness of 10 microns. An epoxy resin was applied to the photosensitive resin cured film of the above sample, followed by the insertion of pins. An adhesion test was then performed using a take-up test machine (Quad Group, Sebastian 5). The evaluation was performed according to the following criteria. Rating: Adhesion strength 70 MPa or higher: Excellent adhesion 50 MPa or higher - less than 70 MPa: Good adhesion 30 MPa or more - less than 50 MPa: Adhesion possible Less than 30 MPa: Adhesion not possible

[0239] 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. The mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring 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 with stirring. Subsequently, 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 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.

[0240] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of crude polymer. The 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.

[0241] 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.

[0242] 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 50.2 g of p-phenylenediamine was used instead of 93.0 g 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 19,000.

[0243] 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 4,4'-oxydiphthalic acid dianhydride was replaced with fluorenic acid dianhydride (229.2 g) and 4,4'-oxydianiline was replaced with 2,2'-bis(trifluoromethyl)benzidine (TFMB) (148.5 g), to obtain polymer (A-4). The molecular weight of polymer (A-4) was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was 12,000.

[0244] Production Example 5: (A) Synthesis of Polymer A-5 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-5). The weight-average molecular weight (Mw) of polymer (A-5) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 21,000.

[0245] Manufacturing Example 6: (E) Synthesis of thermal base generator E-1 100 g of diethylene glycol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol were added to a 1 L round-bottom flask and mixed with a stirrer to form a homogeneous solution, which was then cooled to below 5°C in ice water. To this solution, 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 120 g of ethanol was added dropwise using a dropping funnel. During this process, the dropping rate was adjusted to maintain the reaction solution temperature below 50°C. Two hours after the completion of the dropwise addition, the reaction solution was concentrated under reduced pressure at 50°C for 3 hours to obtain the target compound E-1.

[0246] <Example 1> 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) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photopolymerization initiator B-1) as a photopolymerization initiator, (C) 1.5 g of KBM-403, and (D) 150 g of the organic solvent γ-butyllactone (hereinafter referred to as GBL) were dissolved in the solution. 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 3.

[0247] <Examples 2-13, Comparative Examples 1-3> A negative-type photosensitive resin composition was prepared in the same manner as in Example 1, except that it was prepared with the components and mixing ratios shown in Table 3, and evaluated in the same manner as in Example 1. The results are shown in Table 3. The compounds listed in Table 3 are as follows:

[0248] B-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime C-1:3-Glycidoxypropyltrimethoxysilane (KBM-403) C-2: N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) C-3:3-Uleidopropyltriethoxysilane (KBE-585) C-4:3-Isocyanate-propyltriethoxysilane (KBE-9007) C-5:3-aminopropyltrimethoxysilane (KBM-903) D-1: γ-butyllactone (hereinafter referred to as GBL) D-2: Dimethyl sulfoxide (DMSO) E-1: Compound represented in Manufacturing Example 5 E-2: 1-(tert-butoxycarbonyl)-4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0249] [Table 3]

[0250] As is clear from Table 3, Examples 1 to 13, which included the (C) silane coupling agent having the specific structure represented by the general formula (1) above, showed higher chemical resistance and resolution compared to Comparative Examples 1 to 3, which did not include the (C) silane coupling agent having the specific structure represented by the general formula (1) above. Furthermore, after high-temperature storage tests, the generation of voids at the interface between the Cu layer and the resin layer was suppressed, and adhesion to the sealing material was also good. [Industrial applicability]

[0251] Industrial applicability of the first invention The photosensitive resin composition of 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.

[0252] Industrial applicability of the second invention 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 negative-type photosensitive resin composition comprising (A) a polyimide precursor having an unsaturated double bond in its side chain, and (B) a photopolymerization initiator having an oxime structure, The IR spectrum when (A) is heated and cured at 230°C is (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500 cm) -1 The absorption peak values ​​in the vicinity are 0.1 to 0.

56. Add 100 mJ / cm to the 100 μM dimethyl sulfoxide solution of (B) mentioned above. 2 A negative-type photosensitive resin composition characterized by having a radical generation amount of 3.0 to 30.0 μM when irradiated with a light source.

2. The aforementioned (1380 cm) -1 (Absorption peak value in the vicinity) / (1500 cm) -1 The negative-type photosensitive resin composition according to claim 1, wherein the absorption peak value in the vicinity is 0.3 to 0.

54.

3. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the amount of radical generation is 5.0 to 30.0 μM.

4. The negative-type photosensitive resin composition according to any one of claims 1 to 3, wherein the amount of radical generation is 8.0 to 30.0 μM.

5. The negative-type photosensitive resin composition according to any one of claims 1 to 4, wherein the amount of radical generation is 10.0 to 30.0 μM.

6. The negative-type photosensitive resin composition according to any one of claims 1 to 5, further comprising (C) a solvent.

7. The polyimide precursor having an unsaturated double bond in the side chain (A) is given by the following general formula (A1): 【Chemistry 1】 [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 Each of these is independently a hydrogen atom, and the following general formula (R1): 【Chemistry 2】 {In the general formula (R1), R 3 , R 4 , and R 5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10. A monovalent organic group represented by the formula), or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R 1 and R 2 are not simultaneously hydrogen atoms.}, The negative photosensitive resin composition according to any one of claims 1 to 6, comprising the structure represented by the formula.

8. In the above general formula (A1), Y is given by the following general formula (Y1): 【Transformation 3】 (In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms, which may contain a halogen atom; a represents an integer from 0 to 4; A independently represents an oxygen atom or a sulfur atom; and B is given by the following formula: 【Chemistry 4】 The negative-type photosensitive resin composition according to claim 7, comprising a structure represented by (one of the types).

9. The negative-type photosensitive resin composition according to any one of claims 1 to 8, wherein the weight-average molecular weight (Mw) of (A) is 15,000 to 38,000.

10. In the above general formula (A1), Y is given by the following formula: 【Transformation 5】 Or the following formula: 【Transformation 6】 A negative-type photosensitive resin composition according to any one of claims 7 to 9, having the structure represented by [the formula shown].

11. In the above general formula (A1), X is given by the following general formula (X1): 【Transformation 7】 (In the formula, Ry represents a monovalent organic group having 1 to 10 carbon atoms, which may each independently contain a halogen atom; a represents an integer from 0 to 4; C is at least one selected from the group consisting of a single bond, an ester bond, an oxygen atom, and a sulfur atom; and D is a single bond, or the following formula: 【Transformation 8】 A negative-type photosensitive resin composition according to any one of claims 7 to 10, comprising a structure represented by )].

12. In general formula (X1), C is an oxygen atom or a sulfur atom, and D is given by the following formula: 【Chemistry 9】 A negative-type photosensitive resin composition according to claim 11, comprising at least one of the following.

13. The above X is given by the following formula: 【Chemistry 10】 Or the following formula: 【Chemistry 11】 A negative-type photosensitive resin composition according to any one of claims 7 to 12, having the structure represented by [the formula shown].

14. The negative-type photosensitive resin composition according to any one of claims 7 to 13, wherein p in the general formula (R1) is 3 to 10.

15. A negative-type photosensitive resin composition according to any one of claims 7 to 14, wherein the weight loss rate of a cured film heated at 230°C for 2 hours is 0.5 to 3.0% when heated at 350°C, and the proportion of the weight loss component derived from R1 and R2 in the general formula (A1) is 60 to 80%.

16. The following general formula (A1): 【Chemistry 12】 [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 Each of these is independently a hydrogen atom, and the following general formula (R1): 【Chemistry 13】 {(In general formula (R1), R 3 , R 4 , and R 5 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 1 and R 2 It is impossible for both to be hydrogen atoms at the same time. The structure is represented by}, and Y is given by the following general formula (Y1): 【Chemistry 14】 (In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms, which may contain a halogen atom; a represents an integer from 0 to 4; A is an oxygen atom or a sulfur atom; and B is given by the following formula: 【Chemistry 15】 (A) A polyimide precursor containing the structure represented by ) ] A negative-type photosensitive resin composition characterized by comprising (B) a photopolymerization initiator having an oxime structure and (C) a solvent.

17. The negative-type photosensitive resin composition according to claim 16, wherein the weight-average molecular weight (Mw) of (A) is 15,000 to 38,000.

18. In the above general formula (A1), Y is given by the following formula: 【Chemistry 16】 Or the following formula: 【Chemistry 17】 A negative-type photosensitive resin composition according to any one of claims 16 or 17, having a structure represented by [the given formula].

19. The IR spectrum when (A) is heated and cured at 230°C is (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500 cm) -1 The absorption peak values ​​in the vicinity are 0.1 to 0.

56. Add 100 mJ / cm to the 100 μM dimethyl sulfoxide solution of (B) mentioned above. 2 A negative-type photosensitive resin composition according to any one of claims 16 to 18, wherein the amount of radicals generated when irradiated is 3.0 to 30.0 μM.

20. The following general formula (A1): [Chemistry 18] [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 Each of these is independently a hydrogen atom, and the following general formula (R1): 【Chemistry 19】 {(In general formula (R1), R 3 , R 4 , and R 5 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 1 and R 2 It is impossible for both to be hydrogen atoms at the same time. The structure is represented by}, where X is the following general formula (X1): 【Chemistry 20】 (In the formula, Ry represents a monovalent organic group having 1 to 10 carbon atoms, which may each independently contain a halogen atom; a represents an integer from 0 to 4; C is at least one selected from the group consisting of a single bond, an ester bond, an oxygen atom, and a sulfur atom; and D is a single bond, or the following formula: 【Chemistry 21】 A polyimide precursor containing the structure represented by ) is one of the types within it. A negative-type photosensitive resin composition characterized by containing (B) a photopolymerization initiator having an oxime structure and (C) a solvent.

21. In general formula (X1), C is an oxygen atom or a sulfur atom, and D is given by the following formula: 【Chemistry 22】 One of the types is the negative-type photosensitive resin composition according to claim 20.

22. The above X is given by the following formula: 【Chemistry 23】 Or the following formula: 【Chemistry 24】 A negative-type photosensitive resin composition according to claim 20 or 21, having a structure represented by [the given formula].

23. The IR spectrum when (A) is heated and cured at 230°C is (1380 cm⁻¹). -1 (Absorption peak value in the vicinity) / (1500 cm) -1 The absorption peak values ​​in the vicinity are 0.1 to 0.

56. Add 100 mJ / cm to the 100 μM dimethyl sulfoxide solution of (B) mentioned above. 2 A negative-type photosensitive resin composition according to any one of claims 20 to 22, wherein the amount of radicals generated when irradiated is 3.0 to 30.0 μM.

24. The photopolymerization initiator having the oxime structure (B) The following general formula (B): 【Chemistry 25】 (In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents an organic group having 1 to 20 carbon atoms, Rc represents an organic group having 1 to 10 carbon atoms, Rd represents an organic group having 1 to 10 carbon atoms, b is an integer from 0 to 2, and Rg represents an organic group having 1 to 4 carbon atoms, and multiple Rg groups may form a ring.) Or general formula (B1): 【Chemistry 26】 (In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents an organic group having 1 to 10 carbon atoms.) A negative-type photosensitive resin composition according to any one of claims 1 to 23, comprising the structure represented by [the formula shown].

25. The negative-type photosensitive resin composition according to any one of claims 6 to 24, wherein the solvent (C) is at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

26. The negative-type photosensitive resin composition according to any one of claims 6 to 25, wherein the solvent (C) is at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, dimethyl succinate, dimethyl malonate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

27. The negative-type photosensitive resin composition according to any one of claims 1 to 26, further comprising (D) a polymerization inhibitor.

28. A method for producing polyimide, comprising curing a negative-type photosensitive resin composition according to any one of claims 1 to 27.

29. The following steps: (1) A coating step of applying the negative-type photosensitive resin composition according to any one of claims 1 to 27 onto a substrate to form a photosensitive resin layer on the substrate, (2) An exposure step of exposing the photosensitive resin layer, (3) A developing step in which the photosensitive resin layer after exposure is developed to form a relief pattern, (4) A heating step in which a hardened relief pattern is formed by heat treatment of the relief pattern, A method for producing a hardened relief pattern, characterized by including [a specific element].

30. A semiconductor device having a cured relief pattern obtained by the manufacturing method described in claim 29.

31. The following general formula (A1); 【Chemistry 27】 [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 Each of these is independently a hydrogen atom, and the following general formula (R1): 【Chemistry 28】 {In general formula (R1), R 3 , R 4 , and R 5 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 1 and R 2 It is impossible for both to be hydrogen atoms at the same time. A cured film obtained by curing a polyimide precursor containing the structure represented by ] The weight loss rate of the cured film when heated at 350°C is 0.5 to 3.0%, and the weight loss component is R in the general formula (A1). 1 , R 2 A cured film in which 60-80% originates from [the specified source].

32. The following general formula (A1); 【Chemistry 29】 [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 Each of these is independently a hydrogen atom, and the following general formula (R1): 【Transformation 30】 {In general formula (R1), R 3 , R 4 , and R 5 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 1 and R 2 It is impossible for both to be hydrogen atoms at the same time. A cured film obtained by curing a polyimide precursor containing the structure represented by ] The concentration of imide groups in the polyimide in the cured film is 12.0% to 25.0%, A cured film having a weight loss rate of 0.5 to 3.0% when heated at 350°C.

33. IR spectrum (1380 cm⁻¹) -1 (Absorption peak value in the vicinity) / (1500 cm) -1 The cured film according to claim 31, wherein the absorption peak value in the vicinity is 0.3 to 0.

54.

34. A cured film according to any one of claims 31 to 33, wherein the dielectric loss tangent at 10 GHz is 0.001 to 0.

009.

35. The following general formula (A1); 【Chemistry 31】 [In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 Each of these is independently a hydrogen atom, and the following general formula (R1): 【Chemistry 32】 {In general formula (R1), R 3 , R 4 , and R 5 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.} is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 1 and R 2 It is impossible for both to be hydrogen atoms at the same time. A cured film obtained by curing a polyimide precursor containing the structure represented by ] The concentration of imide groups in the polyimide in the cured film is 12.0% to 25.0%, A method for manufacturing a cured film, wherein the weight loss rate of the cured film when heated at 350°C is 0.5 to 3.0%, A coating process that forms a film containing a photosensitive polyimide precursor. A curing step to polyimide a film containing the polyimide precursor. Having at least, The curing step includes a heating step at 150 to 250°C, and is a method for producing a polyimide cured film.

Images