Photosensitive resin composition, cured film and electronic device

Abstract

To provide a photosensitive resin composition capable of obtaining a cured film with improved flux wettability.SOLUTION: Provided is a photosensitive resin composition comprising an alkali-soluble resin, a surfactant, and a photosensitive agent, in which, when time-of-flight secondary ion mass spectrometry is performed on a cured film produced by a method 1, peaks derived from the surfactant (B) are detected on the cured film. In the method 1, the photosensitive resin composition is applied onto a silicon wafer using a spin coater, and then prebaked at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The coating film is irradiated with and exposed to i-line light at a dose of 500 mJ / cm2 through a line-and-space pattern mask, developed with an alkaline developer at 23°C for 100 seconds, rinsed with pure water for 60 seconds, and then cured in an oven at 230°C for 90 minutes to obtain a cured film having an opening with a width of 25 μm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a cured film, and an electronic device. [Background technology]

[0002] A cured film obtained by exposing a photosensitive resin composition to light is sometimes used as a permanent film constituting an electronic device. Techniques relating to such photosensitive resin compositions include, for example, those described in Patent Document 1.

[0003] Patent Document 1 aims to provide a photosensitive resin composition that has excellent chemical resistance while maintaining high sensitivity. The photosensitive resin composition described in Patent Document 1 includes: (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) a polymer having (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group; (2) a polymer having (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group; (B) a photoacid generator; (C) an aromatic heterocyclic compound; and (D) a solvent; wherein the aromatic heterocyclic compound (C) has a molecular weight of 1,000 or less, contains at least one nitrogen atom in the aromatic ring, and contains at least two coordinating atoms in the aromatic ring. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-189006 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a photosensitive resin composition that can provide a cured film with improved flux wettability. [Means for solving the problem]

[0006] According to the present invention, there are provided the following photosensitive resin composition, cured film, and electronic device.

[0007] [1] A photosensitive resin composition comprising an alkali-soluble resin (A), a surfactant (B), and a photosensitizer (C), A photosensitive resin composition, in which a peak derived from the surfactant (B) is detected on a surface of a cured film having an opening with a width of 25 μm, which is produced by the following method 1, when the surface of the cured film is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS). (Method 1) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. Next, the obtained coating film is irradiated with i-rays at a dose of 500 mJ / cm through a mask with a line and space pattern of 25 μm in width. 2 The exposed coating film is then developed with an alkaline developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 23°C for 100 seconds, rinsed with pure water for 60 seconds, and then cured in an oven at 230°C for 90 minutes to obtain a cured film having openings with a width of 25 μm. [2] The photosensitive resin composition according to [1], wherein the ratio (X1 / X2) of the peak intensity (X1) derived from the surfactant (B) on a cured film obtained by the method 1 to the peak intensity (X2) derived from the surfactant (B) on a cured film obtained by the method 2 below is 0.01 or more and 0.30 or less. (Method 2) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film. [3] The photosensitive resin composition according to [1] or [2], wherein the surfactant (B) comprises one or more selected from the group consisting of a silicon-based surfactant (B1) and a fluorine-based surfactant (B2). [4] The photosensitive resin composition according to [3], wherein the silicon surfactant (B1) contains a polyether-modified polydimethylsiloxane (b). [5] When time-of-flight secondary ion mass spectrometry (TOF-SIMS) was performed on the surface of the cured film produced by the method 1, C3H9Si derived from the polyether-modified polydimethylsiloxane (b) was + The peak is detected, Within 1 nm from the surface of the cured film in the depth direction, C3H9Si + The photosensitive resin composition according to [4], wherein the peak intensity (X1) of [6] When time-of-flight secondary ion mass spectrometry (TOF-SIMS) was performed on the surface of the cured film prepared by the following method 2, C3H9Si derived from the polyether-modified polydimethylsiloxane (b) was found. + The peak is detected, Within 1 nm from the surface of the cured film in the depth direction, C3H9Si + The photosensitive resin composition according to [4] or [5], wherein the peak intensity (X2) of (Method 2) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film. [7] When the surface of the cured film produced by the method 1 was subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), F derived from the fluorine-based surfactant (B2) was detected. - The peak is detected, F within 1 nm in the depth direction from the surface of the cured film - The photosensitive resin composition according to [3], wherein the peak intensity (X1) of [8] When time-of-flight secondary ion mass spectrometry (TOF-SIMS) was performed on the surface of the cured film prepared by the following method 2, F derived from the fluorine-based surfactant (B2) was detected. - The peak is detected, F within 1 nm in the depth direction from the surface of the cured film - The photosensitive resin composition according to [3] or [7], wherein the peak intensity (X2) of (Method 2) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film. [9] The photosensitive resin composition according to any one of [4] to [6], wherein the polyether-modified polydimethylsiloxane (b) has a weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography, of 1,000 or more and 5,000 or less.

[10] The photosensitive resin composition according to any one of [4] to [6] and [9], wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene of the polyether-modified polydimethylsiloxane (b) measured by gel permeation chromatography is 1 or more and 10 or less.

[11] The photosensitive resin composition according to any one of [4] to [6], [9] and

[10] , wherein the polyether-modified polydimethylsiloxane (b) has a weight-average molecular weight of the maximum peak of a molecular weight distribution in terms of polystyrene measured by gel permeation chromatography of 1,000 or more and 5,000 or less.

[12] The photosensitive resin composition according to any one of [4] to [6], [9],

[10] and

[11] , wherein the polyether-modified polydimethylsiloxane (b) comprises a polyether-modified polydimethylsiloxane represented by the following general formula (1): [ka] (In the general formula (1), m is an average value of 1 or more and 5 or less, p is an average value of 1 or more and 10 or less, q is an average value of 0 or more and less than 1, and R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)

[13]

[12] The photosensitive resin composition according to

[12] , wherein, in the general formula (1), x is 1 or more and 50 or less on average, and y is 1 or more and 10 or less on average.

[14] The photosensitive resin composition according to

[12] or

[13] , wherein x / y in the general formula (1) is 1 or more and 5 or less.

[15] The photosensitive resin composition according to any one of [1] to

[14] , wherein the content of the surfactant (B) in the photosensitive resin composition is 130 ppm or more and 3000 ppm or less with respect to the total amount of the photosensitive resin composition.

[16] The photosensitive resin composition according to any one of [1] to

[15] , wherein the alkali-soluble resin (A) has a weight average molecular weight (Mw) of 5,000 or more and 70,000 or less in terms of polystyrene, as measured by gel permeation chromatography.

[17] The photosensitive resin composition according to any one of [1] to

[16] , wherein the content of the alkali-soluble resin (A) in the photosensitive resin composition is 30 parts by mass or more and 95 parts by mass or less, when the total solid content of the photosensitive resin composition is 100 parts by mass.

[18] The photosensitive resin composition according to any one of [1] to

[17] , further comprising a solvent (D).

[19] The photosensitive resin composition according to

[18] , wherein the solvent (D) contains one or more selected from the group consisting of γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, propylene glycol monomethyl ether, 3-methyl-2-oxazolidinone, 3-methoxy-N,N-dimethylpropanamide, and propylene glycol monomethyl ether acetate.

[20] A cured film comprising a cured product of the photosensitive resin composition according to any one of [1] to

[19] . [twenty one] An electronic device comprising the cured film according to

[20] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a photosensitive resin composition that can give a cured film with improved wettability with a flux. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a diagram showing an example of an electronic device including the photosensitive resin composition of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expression "a to b" in the description of a range of numerical values ​​means that the range is from a to b, unless otherwise specified.

[0011] <Photosensitive resin composition> The photosensitive resin composition of the present embodiment is a photosensitive resin composition containing an alkali-soluble resin (A), a surfactant (B), and a photosensitizer (C), When time-of-flight secondary ion mass spectrometry (TOF-SIMS) is performed on the surface of a cured film having an opening with a width of 25 μm, which is prepared by the following method 1, a peak derived from the surfactant (B) is detected on the cured film. (Method 1) The photosensitive resin composition of this embodiment is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. Next, the obtained coating film is irradiated with i-rays at a dose of 500 mJ / cm through a mask with a line-and-space pattern of 25 μm in width. 2The exposed coating film is then developed with an alkaline developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 23°C for 100 seconds, rinsed with pure water for 60 seconds, and then cured in an oven at 230°C for 90 minutes to obtain a cured film having openings with a width of 25 μm.

[0012] In this embodiment, the peak derived from the surfactant (B) on the cured film can be identified by, for example, performing time-of-flight secondary ion mass spectrometry (TOF-SIMS) under the following measurement conditions and analyzing the fragment structure of the surfactant (B) from the detection tendency of the mass spectrum. When the surfactant (B) contains a polyether-modified polydimethylsiloxane (b), C3H9Si + The peak (mass-to-charge ratio: 73) is a peak derived from surfactant (B). When surfactant (B) contains fluorine-based surfactant (B2), F - The peak (mass charge ratio: 19) is a peak derived from surfactant (B). (Measurement conditions) Equipment: TRIFT IV (Physical Electronics) Ion species: Bi 3++ Acceleration voltage: 30 kV Detection depth: 1nm Analysis range: 100 μm square ·Measurement secondary ions: positive and negative

[0013] When the surface of the cured film produced by Method 1 is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), a peak derived from the surfactant (B) is detected. When the peak intensity derived from the surfactant (B) within 1 nm in the depth direction from the surface of the cured film is designated as X1, from the viewpoint of further improving the flux wettability of the obtained cured film, X1 is preferably 50≦X1≦50,000, more preferably 150≦X1≦40,000, even more preferably 250≦X1≦30,000, and even more preferably 350≦X1≦25,000. The X1 can be adjusted by, for example, adjusting the type and amount of the surfactant (B) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0014] When the surfactant (B) contains the polyether-modified polydimethylsiloxane (b) described below, when the surface of the cured film produced by the method 1 is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), C3H9Si derived from the polyether-modified polydimethylsiloxane (b) is detected. + The peak of C3H9Si was detected within 1 nm from the surface of the cured film. + From the viewpoint of further improving the flux wettability of the obtained cured product, the peak intensity (X1) of is preferably 50≦X1≦1100, more preferably 150≦X1≦1000, even more preferably 250≦X1≦900, and still more preferably 350≦X1≦900. The X1 can be adjusted by, for example, adjusting the type and amount of the polyether-modified polydimethylsiloxane (b) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0015] When the surfactant (B) contains a fluorosurfactant (B2), when the surface of the cured film produced by the method 1 is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), F derived from the fluorosurfactant (B2) is detected. - The peak of F was detected within 1 nm from the surface of the cured film. - From the viewpoint of further improving the flux wettability of the obtained cured product, the peak intensity (X1) of The X1 can be adjusted by, for example, adjusting the type and amount of the fluorine-containing surfactant (B2) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0016] When the peak intensity derived from the surfactant (B) on the cured film in the below-described Method 2 is designated as X2, the peak intensity X2 is preferably 3500≦X2≦500000, more preferably 4000≦X2≦400000, even more preferably 5000≦X2≦300000, and still more preferably 5500≦X2≦250000, from the viewpoint of further improving the flux wettability of the obtained cured product. (Method 2) The photosensitive resin composition of this embodiment is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film. The X2 can be adjusted by, for example, adjusting the type and amount of the surfactant (B) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0017] When the surfactant (B) contains a polyether-modified polydimethylsiloxane (b), when the surface of the cured film produced by the method 2 is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), C3H9Si derived from the polyether-modified polydimethylsiloxane (b) is detected. + The peak of C3H9Si was detected within 1 nm from the surface of the cured film. + From the viewpoint of further improving the flux wettability of the obtained cured product, the peak intensity (X2) of is preferably 3500≦X2≦15000, more preferably 4000≦X2≦12000, even more preferably 5000≦X1≦10000, and still more preferably 5500≦X1≦8500. X2 can be adjusted, for example, by adjusting the type and amount of polyether-modified polydimethylsiloxane (b) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0018] When the surfactant (B) contains a fluorosurfactant (B2), when the surface of the cured film produced by the method 2 is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), F derived from the fluorosurfactant (B2) is -The peak of F was detected within 1 nm from the surface of the cured film. - From the viewpoint of further improving the flux wettability of the obtained cured product, the peak intensity (X2) of is preferably 100000≦X2≦500000, more preferably 150000≦X2≦400000, even more preferably 180000≦X2≦350000, and still more preferably 200000≦X2≦300000. The X2 can be adjusted, for example, by adjusting the type and amount of the fluorine-based surfactant (B2) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0019] The ratio (X1 / X2) of the peak intensity (X1) derived from the surfactant (B) on the cured film obtained by Method 1 to the peak intensity (X2) derived from the surfactant (B) on the cured film obtained by Method 2 is preferably 0.01 or more and 0.30 or less, more preferably 0.02 or more and 0.25 or less, even more preferably 0.03 or more and 0.20 or less, and still more preferably 0.05 or more and 0.15 or less, from the viewpoint of further improving the flux wettability of the obtained cured product. The X1 / X2 ratio can be adjusted by, for example, adjusting the type and amount of the surfactant (B) in the photosensitive resin composition, the method for preparing the photosensitive resin composition, and the like.

[0020] Each component of the photosensitive resin composition of this embodiment will be described below.

[0021] (Alkali-soluble resin (A)) The alkali-soluble resin (A) can be selected depending on the physical properties, such as mechanical and optical properties, required for the resin film. Specific examples of the alkali-soluble resin (A) include polyamide resins, polybenzoxazole resins, polyimide resins, phenolic resins, hydroxystyrene resins, and cyclic olefin resins. One or more of these can be used in combination. Of the above specific examples, the alkali-soluble resin (A) preferably includes one or more selected from the group consisting of polyamide resins and polybenzoxazole resins, and more preferably includes polybenzoxazole resins. This improves the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition. Furthermore, improving the physical properties, such as the mechanical strength, of the cured film made from the photosensitive resin composition improves the uniformity of the film thickness and suppresses the occurrence of defects.

[0022] (Polyamide resin, polybenzoxazole resin) The polyamide resin preferably contains an aromatic polyamide containing an aromatic ring in the structural unit of the polyamide, and more preferably contains a structural unit represented by the following formula (PA1): This can improve the physical properties such as mechanical strength of the cured film made of the photosensitive resin composition, thereby improving the uniformity of the film thickness and suppressing the occurrence of defects. In this embodiment, the aromatic ring refers to a benzene ring, a fused aromatic ring such as a naphthalene ring, an anthracene ring, or a pyrene ring, or a heteroaromatic ring such as a pyridine ring or a pyrrole ring. From the viewpoint of further improving the mechanical strength, the polyamide resin of this embodiment preferably contains a benzene ring as the aromatic ring.

[0023] [ka]

[0024] The polyamide resin containing the structural unit represented by the formula (PA1) is a precursor of a polybenzoxazole resin. The polyamide resin containing the structural unit represented by the formula (PA1) can be dehydrated and cyclized to form a polybenzoxazole resin by, for example, heat treatment at a temperature of 150°C to 420°C for 30 minutes to 50 hours. Here, the structural unit of the formula (PA1) is converted into a structural unit represented by the following formula (PBO1) by dehydration and cyclization.

[0025] When the alkali-soluble resin (A) of this embodiment contains a polyamide resin containing a structural unit represented by the formula (PA1), for example, the photosensitive resin composition may be subjected to the heat treatment described above to dehydrate and ring-close the polyamide resin to form a polybenzoxazole resin. That is, when a photosensitive resin composition containing a polyamide resin is subjected to the heat treatment described above, the photosensitive resin composition contains a polybenzoxazole resin. Furthermore, when the alkali-soluble resin (A) contains a polyamide resin containing a structural unit represented by the above formula (PA1), a cured film described below may be produced, and then the cured film may be subjected to the above heat treatment to dehydrate and ring-close the polyamide resin, thereby forming a polybenzoxazole resin. When the polyamide resin is converted into a polybenzoxazole resin by dehydrating and ring-opening the polyamide resin, the mechanical properties and thermal properties can be further improved, and deformation of the cured film can be further suppressed.

[0026] [ka]

[0027] (Polyamide resin, polyimide resin) Furthermore, the polyamide resin may include, for example, a structural unit represented by the following formula (PA2). A polyamide resin containing a structural unit represented by the following formula (PA2) is a precursor of a polyimide resin. The polyamide resin containing a structural unit represented by the following formula (PA2) can be converted into a polyimide resin by dehydration and ring closure, for example, by heat treatment at a temperature of 150°C to 420°C for 30 minutes to 50 hours. Here, the structural unit of the following formula (PA2) becomes a structural unit represented by the following formula (PI1) through dehydration and ring closure. When the alkali-soluble resin (A) of this embodiment is a polyamide resin containing a structural unit represented by the following formula (PA2), the photosensitive resin composition may be subjected to the heat treatment described above to dehydrate and ring-close the resin to form a polyimide resin. That is, the heat-treated photosensitive resin composition contains a polyimide resin as the alkali-soluble resin (A). Furthermore, when the alkali-soluble resin (A) contains a polyamide resin containing a structural unit represented by the following formula (PA2), after producing a resin film and an electronic device as described below, the resin may be subjected to the above-mentioned heat treatment to dehydrate and ring-close the polyimide resin.

[0028] [ka]

[0029] In formula (PA2), R B and R C are preferably each independently an organic group having 1 to 30 carbon atoms.

[0030] [ka] In formula (PI1), R B and R C is the same as the above formula (PA2).

[0031] R in formula (PA2) and formula (PI1) B and R C is preferably an organic group having an aromatic ring. The organic group having an aromatic ring preferably contains a benzene ring, a naphthalene ring, or an anthracene ring, and more preferably contains a benzene ring, which can further improve the dispersibility of the alkali-soluble resin (A) and the wettability of the flux.

[0032] (Method of producing polyamide resin) The polyamide resin can be polymerized, for example, as follows. First, in the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed to polymerize a polyamide. Next, in the low-molecular-weight component removal step (S2), low-molecular-weight components are removed to obtain a polyamide resin containing polyamide as the main component.

[0033] (Polymerization step (S1)) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing a polyamide is not limited, and specific examples include melt polycondensation, an acid chloride method, and direct polycondensation. Instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid dichloride, or active ester-type dicarboxylic acid may be used. Specific examples of a method for obtaining an active ester-type dicarboxylic acid include a method in which a dicarboxylic acid is reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

[0034] The diamine monomer and dicarboxylic acid monomer used in the polymerization of the polyamide resin are described below. The diamine monomer and dicarboxylic acid monomer may each be used alone, or one or more selected from the group consisting of two or more diamine monomers and two or more dicarboxylic acid monomers may be used.

[0035] (diamine monomer) As the diamine monomer used in the polymerization, it is preferable to use a diamine monomer containing an aromatic ring in its structure, and it is more preferable to use a diamine monomer containing a phenolic hydroxyl group in its structure. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled and the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition can be further improved.

[0036] The diamine monomer containing a phenolic hydroxyl group in its structure is preferably a diamine monomer represented by the following formula (DA1). By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the molecular chains of the polyamide resin can form a denser structure. Therefore, it is believed that the molecular structure can be frozen in a coordination where the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound, thereby improving adhesion to the substrate. For example, when a diamine monomer represented by the following formula (DA1) is used, the polyamide resin preferably contains a structural unit represented by the following formula (PA3).

[0037] [ka]

[0038] In formula (DA1), R 4 is preferably a group formed by one or more atoms selected from the group consisting of hydrogen atoms, carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, chlorine atoms, fluorine atoms, and bromine atoms. 5 ~R 10 Preferably, each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.

[0039] [ka]

[0040] In formula (PA3), R4 and R 5 ~R 10 is the same as the above formula (DA1).

[0041] R in formula (DA1) and formula (PA3) 4 is preferably a group formed by one or more atoms selected from the group consisting of hydrogen atoms, carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, chlorine atoms, fluorine atoms and bromine atoms. In addition, R 4 is preferably a divalent group. Here, the divalent group refers to the valence of an atom. That is, R 4 indicates that there are two bonds to other atoms.

[0042] R in formula (DA1) and formula (PA3) 4 If contains a carbon atom, R 4 is preferably a group having 1 to 30 carbon atoms, more preferably a group having 1 to 10 carbon atoms, even more preferably a group having 1 to 5 carbon atoms, and still more preferably a group having 1 to 3 carbon atoms.

[0043] R in formula (DA1) and formula (PA3) 4 If contains a carbon atom, R 4 Specific examples of the alkylene group include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group. The alkylene group may be, for example, a straight-chain alkylene group or a branched-chain alkylene group. Specific examples of the straight-chain alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Specific examples of branched alkylene groups include alkylmethylene groups such as -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; and alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and groups in which two or more arylene groups are bonded together. The halogen-substituted alkylene group and halogen-substituted arylene group are preferably the alkylene group and arylene group described above, in which a hydrogen atom is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. Among these, those in which a hydrogen atom is substituted with a fluorine atom are preferred.

[0044] R in formula (DA1) and formula (PA3) 4 If does not contain carbon atoms, then R 4 Specific examples of the group include groups consisting of oxygen atoms or sulfur atoms.

[0045] R in formula (DA1) and formula (PA3) 5 ~R 10are preferably each independently hydrogen or an organic group having from 1 to 30 carbon atoms, preferably hydrogen or an organic group having from 1 to 10 carbon atoms, more preferably hydrogen or an organic group having from 1 to 5 carbon atoms, even more preferably hydrogen or an organic group having from 1 to 3 carbon atoms, and even more preferably hydrogen or an organic group having from 1 to 2 carbon atoms. This allows the aromatic rings of the polyamide resin to be closely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound to each other in a coordinated manner, freezing the molecular structure and improving adhesion.

[0046] R in formula (DA1) and formula (PA3) 5 ~R 10 Specific examples of the organic group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl; alkenyl groups such as allyl, pentenyl, and vinyl; alkynyl groups such as ethynyl; alkylidene groups such as methylidene and ethylidene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, and anthracenyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl; and alkaryl groups such as tolyl and xylyl.

[0047] The diamine monomer represented by formula (DA1) is preferably one or more selected from the group consisting of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-methylenebis(2-amino-3,6-dimethylphenol), 4,4'-methylenebis(2-aminophenol), 1,1-bis(3-amino-4-hydroxyphenyl)ethane, and 3,3'-diamino-4,4'-dihydroxydiphenyl ether. The use of these diamine monomers allows for a dense arrangement of aromatic rings in the polyamide resin. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound to each other, freezing the molecular structure and improving adhesion. The diamine monomer may be one or a combination of two or more of the above specific examples. The structural formulas of these diamine monomers are shown below.

[0048] [ka]

[0049] (Dicarboxylic acid monomer) As the dicarboxylic acid monomer used in the polymerization, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in its structure. As the dicarboxylic acid monomer containing an aromatic ring, it is preferable to use one represented by the following formula (DC1). By producing a polyamide resin using such a dicarboxylic acid monomer as a raw material, it is possible to control the conformation of the polyamide resin and further improve the dispersibility of the alkali-soluble resin (A) in the mixed solvent. Furthermore, the improved dispersibility can further improve the wettability of the flux.

[0050] [ka]

[0051] In formula (DC1), R 11is preferably a group formed by one or more atoms selected from the group consisting of hydrogen atoms, carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, chlorine atoms, fluorine atoms, and bromine atoms. 12 ~R 19 Preferably, each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.

[0052] For example, when a dicarboxylic acid monomer represented by the above formula (DC1) is used, the polyamide resin typically contains a structural unit represented by the following formula (PA4): 11 , R 12 ~R 19 The definition of is the same as in formula (DC1) above.

[0053] [ka]

[0054] R in formula (DC1) and formula (PA4) 11 is preferably a group formed by one or more atoms selected from the group consisting of hydrogen atoms, carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, chlorine atoms, fluorine atoms and bromine atoms. In addition, R 11 is preferably a divalent group. Here, the divalent group refers to the valence of an atom. That is, R 11 indicates that there are two bonds to other atoms.

[0055] R in formula (DC1) and formula (PA4) 11 If contains a carbon atom, R 11 is preferably a group having 1 to 30 carbon atoms, more preferably a group having 1 to 10 carbon atoms, even more preferably a group having 1 to 5 carbon atoms, and still more preferably a group having 1 to 3 carbon atoms.

[0056] R in formula (DC1) and formula (PA4) 11 If contains a carbon atom, R11 Specific examples of the alkylene group include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group. The alkylene group may be, for example, a straight-chain alkylene group or a branched-chain alkylene group. Specific examples of the straight-chain alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Specific examples of branched alkylene groups include alkylmethylene groups such as -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; and alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and groups in which two or more arylene groups are bonded together. Specifically, the halogen-substituted alkylene group and the halogen-substituted arylene group may be the alkylene group and the arylene group described above, in which a hydrogen atom has been substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. Among these, it is preferable to use a group in which a hydrogen atom has been substituted with a fluorine atom.

[0057] R in formula (DC1) and formula (PA4) 11 If does not contain carbon atoms, then R 11 Specific examples of the group include groups consisting of oxygen atoms or sulfur atoms.

[0058] R in formula (DC1) and formula (PA4) 12 ~R 19are preferably each independently hydrogen or an organic group having 1 to 30 carbon atoms, more preferably hydrogen or an organic group having 1 to 10 carbon atoms, even more preferably hydrogen or an organic group having 1 to 5 carbon atoms, even more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and even more preferably hydrogen.

[0059] R in formula (DC1) and formula (PA4) 12 ~R 19 Specific examples of the organic group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl; alkenyl groups such as allyl, pentenyl, and vinyl; alkynyl groups such as ethynyl; alkylidene groups such as methylidene and ethylidene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, and anthracenyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl; and alkaryl groups such as tolyl and xylyl.

[0060] Specific examples of dicarboxylic acid monomers that can be used include diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, and 4,4'-biphenyl dicarboxylic acid. Among the specific examples listed above, diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid is preferred, and diphenyl ether 4,4'-dicarboxylic acid is even more preferred. This allows the aromatic rings of the polyamide resin to be densely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound to each other in a coordinated manner, freezing the molecular structure and improving adhesion.

[0061] It is preferable to modify the amino groups present at the terminals of the polyamide resin simultaneously with or after the polymerization step (S1). The modification can be carried out, for example, by reacting a diamine monomer or a polyamide resin with a specific acid anhydride or a specific monocarboxylic acid. Therefore, it is preferable that the polyamide resin has terminal amino groups modified with a specific acid anhydride or a specific monocarboxylic acid. The specific acid anhydride and the specific monocarboxylic acid have one or more functional groups selected from the group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. Furthermore, the specific acid anhydride and the specific monocarboxylic acid preferably contain, for example, a nitrogen atom. This improves the wettability of the photosensitive resin composition with metal after post-baking.

[0062] Specific examples of the specific acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, HET anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, etc. As the specific acid anhydride, one or more of the above specific examples can be used in combination.

[0063] When the amino group at the terminal of a polyamide resin is modified with a specific cyclic acid anhydride, the specific cyclic acid anhydride is ring-opened. After modifying the polyamide resin, the structural unit derived from the specific cyclic acid anhydride may be ring-closed to form an imide ring. Examples of ring-closing methods include heat treatment. Specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, etc. As the specific monocarboxylic acid, one or a combination of two or more of the above specific examples can be used.

[0064] Furthermore, the carboxyl groups present at the terminals of the polyamide resin may be modified simultaneously with or after the polymerization step (S1). The modification can be carried out, for example, by reacting a dicarboxylic acid monomer or a polyamide resin with a specific nitrogen-containing heteroaromatic compound. Therefore, it is preferable that the polyamide resin has terminal carboxyl groups modified with a specific nitrogen-containing heteroaromatic compound. The specific nitrogen-containing heteroaromatic compound has one or more functional groups selected from the group consisting of 1-(5-1H-triazolyl)methylamino, 3-(1H-pyrazolyl)amino, 4-(1H-pyrazolyl)amino, 5-(1H-pyrazolyl)amino, 1-(3-1H-pyrazolyl)methylamino, 1-(4-1H-pyrazolyl)methylamino, 1-(5-1H-pyrazolyl)methylamino, (1H-tetrazol-5-yl)amino, 1-(1H-tetrazol-5-yl)methylamino, and 3-(1H-tetrazol-5-yl)benzamino. This increases the number of lone electron pairs in the photosensitive resin composition. This improves the wettability of the photosensitive resin composition with metals after pre-baking and post-baking. Specific examples of the specific nitrogen atom-containing heteroaromatic compounds include 5-aminotetrazole.

[0065] (Low molecular weight component removal process (S2)) Following the polymerization step (S1), it is preferable to carry out a low-molecular-weight component removal step (S2) to remove the low-molecular-weight components. Specifically, the organic layer containing the mixture of low-molecular-weight components and polyamide resin is concentrated by filtration or the like, and then redissolved in an organic solvent such as water / isopropanol, whereupon the precipitate is filtered off to obtain a polyamide resin from which the low-molecular-weight components have been removed.

[0066] For polyamide resins, it is preferable to prepare a photosensitive resin composition in the form of a varnish without undergoing a process in which the solvent is completely evaporated and the resulting composition becomes dry after the low-molecular-weight component removal process. This prevents the dispersibility of the alkali-soluble resin (A) from decreasing due to interactions between the polyamide resin molecules resulting from amide bonds. This further improves the wettability of the flux.

[0067] (phenolic resin) Specific examples of the phenolic resin include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac resin, and phenol-biphenyl novolac resin; reaction products of phenolic compounds with aldehyde compounds such as novolac-type phenolic resin, resol-type phenolic resin, and cresol novolac resin; and reaction products of phenolic compounds with dimethanol compounds such as phenol aralkyl resin. The phenolic resin may contain one or more of the above specific examples.

[0068] The phenol compound used in the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the dimethanol compound is not limited. Specific examples of such phenolic compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; alkylphenols such as isopropylphenol, butylphenol, and p-tert-butylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, and phloroglucinol; and biphenyl phenols such as 4,4'-biphenol. One or more of the above specific examples can be used as the phenolic compound.

[0069] The aldehyde compound used in the reaction product of the phenol compound and the aldehyde compound is not limited as long as it is a compound having an aldehyde group. Specific examples of such aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde, etc. As the aldehyde compound, one or more of the above specific examples can be used.

[0070] The dimethanol compound used in the reaction product of the phenol compound and the dimethanol compound is not limited. Specific examples of such dimethanol compounds include dimethanol compounds such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3,3'-biphenyldimethanol, 2,6-naphthalenedimethanol, and 2,6-bis(hydroxymethyl)-p-cresol; and bis(alkoxymethyl) compounds such as 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, and methyl 2,6-naphthalenedicarboxylate. Examples of the dimethanol compound include bis(halogenoalkyl) compounds such as 1,4-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 3,4'-bis(chloromethyl)biphenyl, 3,3'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 3,4'-bis(bromomethyl)biphenyl, and 3,3'-bis(bromomethyl)biphenyl, and biphenyl aralkyl compounds such as 4,4'-bis(methoxymethyl)biphenyl and 4,4'-bis(methoxymethyl)biphenyl. The dimethanol compound may be one or more of the above specific examples.

[0071] (hydroxystyrene resin) The hydroxystyrene resin is not limited, and specifically, a polymerization reaction product or copolymerization reaction product obtained by polymerizing or copolymerizing one or more selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene, and styrene derivatives can be used. Specific examples of the hydroxystyrene derivatives and styrene derivatives include those in which hydrogen atoms in the aromatic rings of hydroxystyrene and styrene are substituted with monovalent organic groups. Examples of the monovalent organic groups substituting the hydrogen atoms include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; alkylidene groups such as methylidene and ethylidene; cycloalkyl groups such as cyclopropyl; and heterocyclic groups such as epoxy and oxetanyl.

[0072] (Cyclic olefin resin) The cyclic olefin resin is not limited, and specifically, a polymerization reaction product or copolymerization reaction product obtained by polymerizing or copolymerizing one or more members selected from the group consisting of norbornene and norbornene derivatives can be used. Specific examples of norbornene derivatives include norbornadiene, bicyclo[2.2.1]-hept-2-ene (trivial name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride.

[0073] The content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 30 to 95 parts by mass, more preferably 40 to 90 parts by mass, even more preferably 50 to 85 parts by mass, and still more preferably 60 to 85 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition, which improves the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition and further improves the wettability of the flux. In the present embodiment, the total solid content of the photosensitive resin composition refers to the total of the components contained in the photosensitive resin composition excluding the solvent.

[0074] The weight average molecular weight (Mw) of the alkali-soluble resin (A) in terms of polystyrene, measured by gel permeation chromatography, is preferably 5,000 or more and 70,000 or less, more preferably 6,000 or more and 65,000 or less, and even more preferably 7,000 or more and 60,000 or less, from the viewpoint of further improving the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition.

[0075] (Surfactant (B)) The surfactant (B) of this embodiment preferably includes one or more surfactants selected from the group consisting of silicon-based surfactants (B1) and fluorine-based surfactants (B2).

[0076] The silicone surfactant (B1) of this embodiment preferably contains a polyether-modified polydimethylsiloxane (b). The polyether-modified polydimethylsiloxane (b) preferably contains a polyether-modified polydimethylsiloxane represented by the following general formula (1). This can further improve the wettability of the flux when producing a photosensitive resin composition. Furthermore, the polyether-modified polydimethylsiloxane represented by the following general formula (1) has a helical structure in the polydimethylsiloxane chain, which is the main chain, and the dimethyl groups and polyether-modifying groups, which are side chains, are arranged on the surface side of the helical structure. This has the advantage that the properties of the polyether-modified polydimethylsiloxane (b) can be controlled by the structure of the side chains.

[0077] [ka]

[0078] In general formula (1), m preferably has an average value of 1 or more and 5 or less, p preferably has an average value of 1 or more and 10 or less, and q preferably has an average value of 0 or more and less than 1. R preferably represents hydrogen or an alkyl group having 1 to 5 carbon atoms.

[0079] In the general formula (1), x is preferably 1 or more and 50 or less, more preferably 2 or more and 40 or less on average. In general formula (1), y is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less on average. In addition, in the general formula (1), the ratio of x to y (x / y) is preferably 1 or more and 5 or less, more preferably 1.2 or more and 4 or less. When x, which represents a dimethyl group in general formula (1), is within the above range, the surface tension of the entire photosensitive resin composition can be appropriately reduced. Furthermore, when x / y is within the above range, the compatibility of the polyether-modified polydimethylsiloxane (b), the alkali-soluble resin (A), the solvent (D), and the photosensitizer (C) is improved. Furthermore, the more polar (hydrophilic) the polyether-modifying group, the more stabilized the foam and the lower the defoaming properties. Conversely, the less polar (hydrophobic) the polyether-modifying group, the lower the foam stability and the better the defoaming properties. When m, p, and q in general formula (1) are equal to or greater than the lower limit values, the side chains of the polyether-modified polydimethylsiloxane (b) become appropriately non-polar (hydrophobic), which reduces foam stability and improves defoaming properties. When m, p, and q in general formula (1) are equal to or less than the upper limit values, the compatibility of the polyether-modified polydimethylsiloxane (b) with the solvent (D), particularly γ-butyrolactone described below, is improved, resulting in further improved defoaming properties.

[0080] In general formula (1), m is preferably an average value of 1 or more and 5 or less, more preferably 2 or more and 4 or less. p is preferably an average value of 1 or more and 10 or less, more preferably 3 or more and 9 or less, even more preferably 4 or more and 9 or less, and even more preferably 5 or more and 9 or less. q is preferably an average value of 0 or more and less than 1. R preferably represents hydrogen or an alkyl group having 1 to 5 carbon atoms, more preferably hydrogen or a methyl group, and even more preferably hydrogen. When m, p, and q are within the above ranges, the polyether-modified polydimethylsiloxane (b) as a whole becomes suitably non-polar (hydrophobic), which further improves the defoaming properties of the photosensitive resin composition. At the same time, the polyether-modified polydimethylsiloxane (b) becomes suitably polar (hydrophilic), which allows it to be dissolved in an aqueous solvent.

[0081] Polyether-modified polydimethylsiloxane (b) can be synthesized from a polyether compound and polydimethylsiloxane. m, p, q, x, and y in general formula (1) can be adjusted by adjusting the type and mixing ratio of the polyether compound and polydimethylsiloxane used. The m, p, q, x, and y in general formula (1) can be determined from the structures of the polyether compound and polydimethylsiloxane used in the synthesis of polyether-modified polydimethylsiloxane (b). In addition, the m, p, q, x, and y in general formula (1) can also be identified by known polymer structure analysis techniques such as NMR, IR, pyrolysis GC-MS, TOF-SIMS, and LC-TOF / MS.

[0082] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene of the polyether-modified polydimethylsiloxane (b), measured by gel permeation chromatography, is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less, even more preferably 2 or more and 7 or less, even more preferably 2 or more and 6 or less, even more preferably 2 or more and 4 or less, and even more preferably 2 or more and 3 or less, from the viewpoint of further improving the flux wettability of the resulting cured product.

[0083] The polystyrene-equivalent weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (b), measured by gel permeation chromatography, is preferably 1,000 or more and 5,000 or less, more preferably 1,200 or more and 4,000 or less, even more preferably 1,300 or more and 3,000 or less, even more preferably 1,400 or more and 2,500 or less, and even more preferably 1,500 or more and 2,000 or less. The polyether-modified polydimethylsiloxane (b) can be used singly or in combination of two or more. When two or more polyether-modified polydimethylsiloxanes (b) are used, it is sufficient that the weight average molecular weight (Mw) of one of the polyether-modified polydimethylsiloxanes (b) is within the above range, but it is preferable that the weighted average value of the weight average molecular weights (Mw) of the polyether-modified polydimethylsiloxanes (b) is within the above range. When the weight-average molecular weight of the polyether-modified polydimethylsiloxane (b) is within the above range, the wettability of the flux is further improved. Also, when the weight-average molecular weight of the polyether-modified polydimethylsiloxane (b) is equal to or less than the above upper limit, compatibility with γ-butyrolactone (described later) is improved, and defoaming properties are further improved.

[0084] The weight average molecular weight of the polyether-modified polydimethylsiloxane (b) at the maximum peak of the molecular weight distribution in terms of polystyrene, as measured by gel permeation chromatography, is preferably 1,000 or more and 5,000 or less, more preferably 1,300 or more and 4,000 or less, and even more preferably 1,800 or more and 4,000 or less. When the weight-average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (b) is within the above range, the wettability of the flux is further improved. Also, when the weight-average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (b) is equal to or less than the above upper limit, compatibility with γ-butyrolactone (described later) is improved, and defoaming properties are further improved.

[0085] In this embodiment, the weight-average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (b) can be calculated using a molecular weight distribution curve obtained by GPC (Gel Permeation Chromatography). The weight-average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) is calculated using a polystyrene-equivalent value obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement. The measurement conditions for GPC are, for example, as follows. Apparatus: Tosoh Corporation gel permeation chromatography apparatus HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Flow rate: 0.35mL / min Sample concentration in the measurement solution: 2.0 mg / mL

[0086] The number average molecular weight (Mn) and the weight average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (b) are the same as the weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (b) described above, measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. The weight-average molecular weight of the maximum peak of polyether-modified polydimethylsiloxane (b) can be calculated by peak separation of the chromatogram obtained by gel permeation chromatography (GPC). Peak separation software such as Eco-SEC manufactured by Tosoh Corporation can be used. The maximum peak refers to the peak with the largest integrated value.

[0087] The surface tension (mN / m) of the polyether-modified polydimethylsiloxane (b) is preferably 20 mN / m or more and 40 mN / m or less, more preferably 25 mN / m or more and 35 mN / m or less, and even more preferably 27 mN / m or more and 30 mN / m or less, from the viewpoint of further improving the flux wettability of the resulting cured product. The surface tension (mN / m) of the polyether-modified polydimethylsiloxane (b) is measured using a contact angle meter at 23° C. in a 1% GBL solution. The contact angle meter used can be a DMs-401 (Kyowa Interface Science Co., Ltd.).

[0088] The density (g / mL) of the polyether-modified polydimethylsiloxane (b), measured at 20°C in accordance with ISO 2811-3:2011, is preferably 0.90 g / mL or more and 1.15 g / mL or less, more preferably 0.95 g / mL or more and 1.10 g / mL or less, from the viewpoint of minimizing the content of low-molecular-weight components. The refractive index of the polyether-modified polydimethylsiloxane (b), measured in accordance with DIN 51423, is preferably 1.30 or more and 1.60 or less, more preferably 1.40 or more and 1.50 or less, from the viewpoint of containing as little low-molecular-weight components as possible. The nonvolatile content of the polyether-modified polydimethylsiloxane (b), measured in accordance with ISO 3251:2019 under heating conditions of 105°C for 1 hour, is preferably 85.0% or more, more preferably 87.0% or more, and even more preferably 90.0% or more, from the viewpoint of containing as little low-molecular-weight components as possible.

[0089] The content of the surfactant (B) in the photosensitive resin composition is preferably 130 ppm or more and 3000 ppm or less, more preferably 150 ppm or more and 1500 ppm or less, even more preferably 200 ppm or more and 1000 ppm or less, even more preferably 250 ppm or more and 800 ppm or less, and even more preferably 300 ppm or more and 700 ppm or less, based on the total amount of the photosensitive resin composition. When the content of the surfactant (B) in the photosensitive resin composition is within the above range, the performance balance between the wettability and film thickness uniformity of the flux of the cured product obtained from the photosensitive resin composition can be further improved. The unit (ppm) of the content of the surfactant (B) relative to the total amount of the photosensitive resin composition represents the content (mg) of the surfactant (B) per 1 kg of the total amount of the photosensitive resin composition, i.e., mg / kg.

[0090] The content of the surfactant (B) in the photosensitive resin composition is preferably 60 ppm or more and 1350 ppm or less, more preferably 70 ppm or more and 750 ppm or less, even more preferably 150 ppm or more and 600 ppm or less, even more preferably 170 ppm or more and 500 ppm or less, and even more preferably 200 ppm or more and 450 ppm or less, based on the total solid content of the photosensitive resin composition. When the content of the surfactant (B) in the photosensitive resin composition is within the above range, the performance balance between the wettability and film thickness uniformity of the flux of the cured product obtained from the photosensitive resin composition can be further improved. The unit (ppm) of the content of the surfactant (B) relative to the total solid content of the photosensitive resin composition represents the content (mg) of the surfactant (B) per 1 kg of the total solid content of the photosensitive resin composition, i.e., mg / kg.

[0091] The content of the polyether-modified polydimethylsiloxane (b) in the photosensitive resin composition is preferably 130 ppm or more and 3000 ppm or less, more preferably 150 ppm or more and 1500 ppm or less, even more preferably 200 ppm or more and 1000 ppm or less, even more preferably 250 ppm or more and 800 ppm or less, and even more preferably 300 ppm or more and 700 ppm or less, based on the total amount of the photosensitive resin composition. When the content of the polyether-modified polydimethylsiloxane (b) is within the above range, the performance balance between the wettability and film thickness uniformity of the cured flux obtained from the photosensitive resin composition can be further improved. The unit (ppm) of the content of the polyether-modified polydimethylsiloxane (b) relative to the total amount of the photosensitive resin composition represents the content (mg) of the polyether-modified polydimethylsiloxane (b) per 1 kg of the total amount of the photosensitive resin composition, i.e., mg / kg.

[0092] The content of the polyether-modified polydimethylsiloxane (b) in the photosensitive resin composition is preferably 60 ppm or more and 1350 ppm or less, more preferably 70 ppm or more and 750 ppm or less, even more preferably 150 ppm or more and 600 ppm or less, even more preferably 170 ppm or more and 500 ppm or less, and even more preferably 200 ppm or more and 450 ppm or less, based on the total solid content of the photosensitive resin composition. When the content of the polyether-modified polydimethylsiloxane (b) in the photosensitive resin composition is within the above range, the performance balance between the wettability and film thickness uniformity of the cured flux obtained from the photosensitive resin composition can be further improved. The unit (ppm) of the content of the polyether-modified polydimethylsiloxane (b) relative to the total solid content of the photosensitive resin composition represents the content (mg) of the polyether-modified polydimethylsiloxane (b) per 1 kg of the total solid content of the photosensitive resin composition, i.e., mg / kg.

[0093] As the fluorine-containing surfactant (B2), any known fluorine-containing surfactant used in this technical field can be used. Examples of the fluorine-based surfactant include, but are not limited to, commercially available fluorine-based surfactants such as F-TOP EF301, EF-TOP EF303, and EF-TOP EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megafac F171, F172, F173, F177, F444, F470, F471, F475, F482, and F477 (manufactured by DIC Corporation), Fluorad FC-430, Fluorad FC-431, Novec FC4430, and Novec FC4432 (manufactured by Sumitomo 3M Limited), and Surflon S-381, S-382, S-383, S-393, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0094] The content of the fluorine-containing surfactant (B2) is preferably 130 ppm or more and 3000 ppm or less, more preferably 140 ppm or more and 1500 ppm or less, even more preferably 150 ppm or more and 1000 ppm or less, even more preferably 180 ppm or more and 500 ppm or less, and even more preferably 200 ppm or more and 400 ppm or less, based on the total amount of the photosensitive resin composition. When the content of the fluorine-based surfactant (B2) is within the above range, the performance balance between the wettability and film thickness uniformity of the flux of the cured product obtained from the photosensitive resin composition can be further improved. The unit (ppm) of the content of the fluorine-containing surfactant (B2) relative to the total amount of the photosensitive resin composition represents the content (mg) of the fluorine-containing surfactant (B2) per 1 kg of the total amount of the photosensitive resin composition, i.e., mg / kg.

[0095] The content of the fluorosurfactant (B2) in the photosensitive resin composition is preferably 60 ppm or more and 1350 ppm or less, more preferably 70 ppm or more and 750 ppm or less, even more preferably 75 ppm or more and 500 ppm or less, even more preferably 90 ppm or more and 250 ppm or less, and even more preferably 100 ppm or more and 200 ppm or less, based on the total solid content of the photosensitive resin composition. When the content of the fluorine-containing surfactant (B2) in the photosensitive resin composition is within the above range, the performance balance between the wettability and film thickness uniformity of the flux of the cured product obtained from the photosensitive resin composition can be further improved. The unit (ppm) of the content of the fluorosurfactant (B2) relative to the total solid content of the photosensitive resin composition represents the content (mg) of the fluorosurfactant (B2) per 1 kg of the total solid content of the photosensitive resin composition, i.e., mg / kg.

[0096] (Photosensitizer (C)) As the photosensitizer (C), a photoacid generator that generates an acid by absorbing light energy can be used. Specific examples of photoacid generators include diazoquinone compounds, diaryliodonium salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonate compounds, 2,6-bis(trichloromethyl)-1,3,5-triazine compounds, and dihydropyridine compounds. Among these, the photosensitizer (C) preferably contains a photosensitive diazoquinone compound. This improves the sensitivity of the photosensitive resin composition. Therefore, the pattern precision can be improved, and the appearance can be further improved. The photoacid generator may contain one or more of the above specific examples. When the photosensitive resin composition is a positive type, the photosensitizer (C) may contain, in addition to the above specific examples, onium salts such as triarylsulfonium salts and sulfonium borate salts, which can further improve the sensitivity of the photosensitive resin composition.

[0097] Examples of diazoquinone compounds are shown below using chemical formulas.

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] In each of the above diazoquinone compounds, Q is a structure represented by the following formula (a), (b), or (c), or a hydrogen atom, provided that at least one of Q in each diazoquinone compound is a structure represented by the following formula (a), (b), or (c). Q of the diazoquinone compound preferably includes the following formula (a) or (b), which can improve the transparency of the photosensitive resin composition and therefore the appearance of the photosensitive resin composition.

[0104] [ka]

[0105] The lower limit of the content of the photosensitizer (C) in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (A), which allows the photosensitive resin composition to exhibit appropriate sensitivity. The upper limit of the content of the photosensitizer (C) in the photosensitive resin composition is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A), which can prevent the photosensitive resin composition from being repelled by metal materials present on the surface of the substrate of the semiconductor device.

[0106] (Solvent (D)) The photosensitive resin composition of this embodiment preferably further contains a solvent (D). The solvent (D) preferably contains at least one selected from the group consisting of γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), propylene glycol monomethyl ether (PGME), 3-methyl-2-oxazolidinone, 3-methoxy-N,N-dimethylpropanamide, and propylene glycol monomethyl ether acetate (PGMEA). From the viewpoint of further improving the flux wettability of the resulting cured product, the solvent (D) more preferably contains one selected from the group consisting of γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), and 3-methyl-2-oxazolidinone, and even more preferably contains γ-butyrolactone. γ-Butyrolactone is compatible with the polyether-modified polydimethylsiloxane (b) described above in that it can make the surface tension of the entire photosensitive resin composition more appropriate and can make the polarity of the polyether-modified polydimethylsiloxane (b) in the photosensitive resin composition more appropriate, and therefore can further improve the defoaming properties.

[0107] The solvent (D) may contain other solvents in addition to those mentioned above. Examples of other solvents include urea-based solvents such as N,N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-dimethylpropyleneurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea; and tetrahydrofurfuryl alcohol. Examples of suitable solvents include alcohol-based solvents such as benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol; ketone-based solvents such as cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone; carbonate-based solvents such as ethylene carbonate and propylene carbonate; sulfone-based solvents such as dimethyl sulfoxide (DMSO) and sulfolane; ester-based solvents such as methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate; and aromatic hydrocarbon-based solvents such as mesitylene, toluene, and xylene. The solvents may be selected from the above specific examples, and may be used alone or in combination of two or more.

[0108] From the viewpoint of further improving the coatability of the photosensitive resin composition, the content of the solvent (D) is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, when the total amount of the photosensitive resin composition is taken as 100% by mass.

[0109] In the photosensitive resin composition of the present embodiment, the total content of the alkali-soluble resin (A), surfactant (B), photosensitizer (C), and solvent (D) is preferably 50% by mass or more and 100% by mass or less, more preferably 55% by mass or more and 100% by mass or less, even more preferably 60% by mass or more and 99% by mass or less, and still more preferably 65% ​​by mass or more and 99% by mass or less, when the total amount of the photosensitive resin composition is taken as 100% by mass, from the viewpoint of further improving the flux wettability of the resulting cured product.

[0110] In the photosensitive resin composition of the present embodiment, the total content of the alkali-soluble resin (A) and the surfactant (B) is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, when the total amount of the photosensitive resin composition is taken as 100% by mass, from the viewpoint of further improving the flux of the obtained cured product.

[0111] The photosensitive resin composition of the present embodiment may further contain additives such as an adhesion aid, a thermal crosslinking agent, an antioxidant, a dissolution promoter, a filler, and a sensitizer.

[0112] (adhesion aid) The photosensitive resin composition of this embodiment may further contain an adhesion aid. The adhesion aid may be one selected from the group consisting of triazole compounds, aminosilanes, imide compounds, epoxysilanes, (meth)acrylicsilanes, and reaction products of epoxy compounds and aminotriazoles. This improves the affinity of the photosensitive resin composition with metal members.

[0113] (thermal crosslinking agent) The photosensitive resin composition of the present embodiment may further contain a thermal crosslinking agent, which can further improve the mechanical properties of the cured product of the photosensitive resin composition. Examples of the thermal crosslinking agent include compounds having a methylol group, phenols, compounds having an alkoxymethyl group, methylol melamine compounds, alkoxy melamine compounds, alkoxymethyl glycoluril compounds, methylol urea compounds, cyano compounds, isocyanate compounds, epoxy group-containing compounds, maleimide compounds, xylene derivatives, etc. As the thermal crosslinking agent, one or a combination of two or more of the above specific examples can be used.

[0114] (antioxidant) The photosensitive resin composition of this embodiment may further contain an antioxidant. As the antioxidant, at least one selected from a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be used. The antioxidant can suppress oxidation of the resin film formed from the photosensitive resin composition.

[0115] (solubility enhancer) The photosensitive resin composition of the present embodiment may further contain a dissolution promoter. The dissolution promoter is a component that can improve the solubility of the exposed portion of a coating film formed using the photosensitive resin composition in a developer and reduce scumming during patterning. As such a dissolution promoter, a compound having a phenolic hydroxyl group is preferred.

[0116] When the alkali-soluble resin (A) contains a polybenzoxazole resin having an aromatic ring or a polyimide resin having an aromatic ring, the dissolution promoter preferably contains one having a biphenol skeleton or a bisphenol A skeleton, which allows the skeleton of the alkali-soluble resin (A) to interact with the dissolution promoter, thereby further improving the dispersibility of the alkali-soluble resin (A).

[0117] (filler) The photosensitive resin composition of the present embodiment may further contain a filler. As the filler, an appropriate filler can be selected depending on the mechanical properties and thermal properties required for the resin film formed from the photosensitive resin composition, and specific examples thereof include inorganic fillers and organic fillers. Examples of inorganic fillers include silica, metal compounds, talc, clay, mica, glass fiber, etc. Specific examples of organic fillers include organosilicone powder, polyethylene powder, etc. As the filler, one or a combination of two or more of the above may be used.

[0118] (Preparation of Photosensitive Resin Composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and any known method can be used depending on the components contained in the photosensitive resin composition. For example, the photosensitive resin composition can be prepared by dissolving the alkali-soluble resin (A) and the photosensitizer (C) in the solvent (D), adding the surfactant (B), and further stirring. This process produces a photosensitive resin composition in the form of a varnish. Furthermore, it is preferable to include a degassing treatment in order to further improve the flux wettability of the resulting cured product.

[0119] (cured film) The photosensitive resin composition of this embodiment is used to form a cured film for semiconductor devices such as wafer level packages and panel level packages. The cured film of this embodiment includes a cured product of the photosensitive resin composition of this embodiment.

[0120] The cured film is obtained by, for example, applying a photosensitive resin composition, prebaking, exposing, and developing the composition, patterning the composition into a desired shape, and then postbaking the composition to harden it. The cured film can be used as a buffer coat film (protective film), an interlayer film, a dam material, or the like for electronic devices. In particular, the cured film can be suitably used as a buffer coat film.

[0121] In the process for producing the cured film, the step of applying the photosensitive resin composition is preferably performed by, for example, spin coating, which allows a more uniform resin film to be formed on the substrate.

[0122] The thickness of the cured film is not particularly limited, but is, for example, from 2 μm to 30 μm, and preferably from 5 μm to 20 μm. After coating the photosensitive resin composition, various methods can be used to remove the solvent (for example, heating), but when used in panel level packages, it is preferable to apply reduced pressure drying in view of the relatively large area. In other words, it is preferable to dry the panel coated with the photosensitive resin composition in a reduced pressure environment (for example, an environment of 30 Pa or less).

[0123] When pre-baking is performed, the conditions are, for example, 70 to 160° C. and about 5 seconds to 30 minutes. For the exposure, electromagnetic waves or particle beams of various wavelengths can be used. For example, ultraviolet rays such as g-rays and i-rays, visible light, lasers, X-rays, electron beams, etc. are used. Ultraviolet rays such as g-rays or i-rays are preferred. The exposure dose is appropriately set depending on the sensitivity of the photosensitive resin composition, and is, for example, 30 to 3000 mJ / cm. 2 The exposure is usually carried out using an appropriate mask pattern. Various developers can be used for development. Examples include alkaline developers such as alkali metal carbonates, alkali metal hydroxides, and tetramethylammonium hydroxide, and organic developers such as dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl acetate. Among these, alkaline developers are preferred, and aqueous solutions of tetramethylammonium hydroxide are particularly preferred. Methods for supplying the developer include spray, paddle, and immersion. For processing large-area panels, the spray method is preferred. The post-baking conditions (curing conditions) are not particularly limited, but for example, are at a temperature of 80° C. or higher and 450° C. or lower for 30 minutes or longer and 300 minutes or shorter.

[0124] (electronic equipment) Next, an example of an electronic device 100 including the photosensitive resin composition of this embodiment will be described. The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, a semiconductor package is obtained by mounting the electronic device 100 on a wiring substrate via bumps 52. The electronic device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer provided on the semiconductor substrate (not shown). The uppermost layer of the multilayer wiring layer includes an interlayer insulating film 30 and a top-layer wiring 34 provided on the interlayer insulating film 30. The top-layer wiring 34 is made of, for example, Al. A passivation film 32 is provided on the interlayer insulating film 30 and the top-layer wiring 34. An opening is provided in a part of the passivation film 32, through which the top-layer wiring 34 is exposed.

[0125] A redistribution layer 40 is provided on the passivation film 32. The redistribution layer 40 includes an insulating layer 42 provided on the passivation film 32, redistribution lines 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the redistribution lines 46. An opening is formed in the insulating layer 42 to expose the top-layer wiring 34. The redistribution lines 46 are formed on the insulating layer 42 and in the openings provided in the insulating layer 42, and are electrically connected to the top-layer wiring 34. An opening is formed in the insulating layer 44 to expose a predetermined region of the redistribution line 46. A bump 52 is formed in the opening in the insulating layer 44, for example, via a UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via the bump 52, for example.

[0126] In this embodiment, one or more of the insulating layer 42 and the insulating layer 44 can be formed of a cured film formed by, for example, curing the above-mentioned photosensitive resin composition. In this case, for example, a coating film formed from the photosensitive resin composition is exposed to ultraviolet light, developed to form a pattern, and then heated and cured to form the insulating layer 42 or the insulating layer 44.

[0127] (Electronic Device Manufacturing Method) The method for manufacturing the electronic device of this embodiment is not particularly limited, and known methods can be used. For example, the method may include a coating film formation step in which the photosensitive resin composition of this embodiment is applied to a substrate to form a coating film, an exposure step in which the formed coating film is exposed to light, a development step in which the exposed coating film is developed, and a heating step in which the coating film remaining after development is heated to harden the coating film and form a cured film. This forms a cured film of the photosensitive resin composition, and this cured film is used as insulating layer 42 or insulating layer 44 that constitutes electronic device 100. Furthermore, the method for producing an electronic device according to this embodiment may further include a step of cleaning the coating film on the back side of the substrate after the coating film forming step. This makes it possible to remove unnecessary coating film that has spread to the back side of the substrate when forming the coating film by spin coating or the like, and to improve the shape of the edges of the cured film formed from the coating film.

[0128] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0129] EXAMPLES The present invention will be explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0130] <Synthesis of alkali-soluble resin (A)> Alkali-soluble resin 1, which is a polyamide resin, was synthesized by the following procedure. Into a four-necked glass separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 170.20 g (0.346 mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 206.58 g (0.800 mol) of diphenyl ether-4,4'-dicarboxylic acid represented by the following formula (DC2) with 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole monohydrate, 4.01 g (0.047 mol) of 5-aminotetrazole, 45.22 g (0.196 mol) of 4,4'-methylenebis(2-aminophenol) represented by the following formula (DA2), and 56.24 g (0.196 mol) of 4,4'-methylenebis(2-amino-3,6dimethylphenol) represented by the following formula (DA3) were placed. Then, 578.3 g of N-methyl-2-pyrrolidone was added to the separable flask, and the raw material components were dissolved. Next, a reaction was carried out for 5 hours at 90°C using an oil bath. Next, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the separable flask, and the reaction was carried out with stirring at 90°C for 2 hours, after which the reaction was terminated by cooling to 23°C.

[0131] The reaction mixture in the separable flask was filtered, and the resulting filtrate was poured into a solution of water / isopropanol = 7 / 4 (volume ratio). The precipitate was then filtered off, thoroughly washed with water, and then dispersed in NMP (N-methylpyrrolidone) without drying, to obtain a solution of the target alkali-soluble resin 1. The weight-average molecular weight Mw of the resulting alkali-soluble resin 1 was 18081.

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] <Synthesis of photosensitizer 1> Photosensitizer 1, a diazoquinone compound, was synthesized by the following procedure. Into a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.04 g (0.026 mol) of a compound represented by the following formula (P-1), 18.81 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 170 g of acetone were placed and stirred to dissolve.

[0136] Next, while cooling the flask in a water bath to prevent the temperature of the reaction solution from exceeding 35°C, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added and the reaction was continued for another 30 minutes. The reaction mixture was then filtered, and the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). The precipitate was then collected by filtration, thoroughly washed with water, and dried under vacuum. This yielded photosensitizer 1, represented by the structure of the following formula (Q-1).

[0137] [ka]

[0138] <Thermal crosslinking agent> Thermal crosslinking agent 1: paraxylene glycol (PXG, manufactured by Ihara Nikkei Chemical Industry Co., Ltd.) <Adhesion aid> Adhesion aid 1: [ka] Adhesion aid 2: [ka] <Solvent> Solvent 1: γ-butyrolactone (GBL) Solvent 2: N-methyl-2-pyrrolidone (NMP) <Surfactant> Fluorosurfactant 1: FC4432, manufactured by 3M Japan Ltd., weight average molecular weight (Mw): 8202, maximum peak molecular weight: 16182, surface tension: 24.2 mN / m

[0139] <Synthesis of polyether-modified polydimethylsiloxane 1> Polyether-modified polydimethylsiloxane 1 was synthesized by referring to Synthesis Example 2 in paragraph 0115 of JP 2002-079109 A, using a polyether compound of the following formula (3) instead of polydimethylsiloxane represented by the following formula (4) and dimethallyl polyether.

[0140] [ka]

[0141] [ka]

[0142] The obtained polyether-modified polydimethylsiloxane 1 had the following general formula (1): m was 3, p was 7, q was 0, x was 4, y was 3, and R was hydrogen. Note that m, p, q, x, and y in general formula (1) were determined from the structures of the polydimethylsiloxane represented by formula (4) and the polyether compound represented by formula (3) used in the synthesis of polyether-modified polydimethylsiloxane 1.

[0143] The polystyrene-equivalent weight average molecular weight of the obtained polyether-modified polydimethylsiloxane 1 was measured by the gel permeation chromatography method described below and was found to be 1730. The polystyrene-equivalent weight average molecular weight at the maximum peak of the molecular weight distribution was 2234, and Mw / Mn was 2.23. The surface tension of polyether-modified polydimethylsiloxane 1 was 29.4 mN / m, the density was 1.037±0.030 g / mL, the refractive index was 1.433±0.010, and the non-volatile content was 96.25±3.75%.

[0144] (density, refractive index and non-volatile content) The density of the polyether-modified polydimethylsiloxane was measured at 20°C in accordance with ISO 2811-3:2011. The refractive index of the polyether-modified polydimethylsiloxane was determined according to DIN 51423. The non-volatile content of polyether-modified polydimethylsiloxane was measured in accordance with ISO 3251:2019 at 105°C for 1 hour.

[0145] (Molecular weight measurement of alkali-soluble resin by gel permeation chromatography) The weight average molecular weight (Mw) of the alkali-soluble resin was measured by the following method. Apparatus: Gel permeation chromatography device manufactured by JASCO Corporation Pump: JASCO Corporation, PU980 Column oven: JASCO CO-965 Sampler: JASCO Corporation, AS-2055 Column: Gelpack GL-83COMDT-5P manufactured by Hitachi High-Technologies Corporation Detector: RI detector for liquid chromatography ·Measurement temperature: 40℃ Solvent: THF ·Flow rate: 0.350mL / min Sample concentration in the measurement solution: 2.0 mg / mL

[0146] (Molecular weight measurement of polyether-modified polydimethylsiloxane and fluorosurfactant by gel permeation chromatography) For the polyether-modified polydimethylsiloxane and the fluorosurfactant, the weight average molecular weight (Mw), number average molecular weight (Mn), and weight average molecular weight of the maximum peak in the polystyrene-equivalent molecular weight distribution were measured by the following methods. Tosoh Corporation gel permeation chromatography system HLC-8320GPC Peak separation software: Eco-SEC, manufactured by Tosoh Corporation Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography ·Measurement temperature: 40℃ Solvent: THF ·Flow rate: 0.35mL / min Sample concentration in the measurement solution: 2.0 mg / mL

[0147] (surface tension) The surface tension (mN / m) of the polyether-modified polydimethylsiloxane and fluorosurfactant was measured at 23°C in a 1% GBL solution using a contact angle meter (DMs-401, Kyowa Interface Science Co., Ltd.).

[0148] (Preparation of Photosensitive Resin Composition) Photosensitive resin compositions of Examples and Comparative Examples were prepared as follows. Each raw material component other than the surfactant was mixed according to the formulation in Table 1 in a stirring vessel (bottom area: 65 cm) so that the total volume of the photosensitive resin composition was 500 mL. 2 The contents were placed in a container and stirred at a temperature of 23°C, with the stirring blade height at 3 cm from the bottom, at a rotation speed of 200 rpm, for a stirring time of 4 hours in a nitrogen atmosphere. After stirring was completed, a surfactant was added according to the formulation in Table 1, and the contents were stirred at a temperature of 23°C, with the stirring blade height at 3 cm from the bottom, at a rotation speed of 200 rpm, for a stirring time of 60 minutes in a nitrogen atmosphere. Subsequently, a degassing treatment was carried out for 24 hours in an atmosphere at a room temperature of 23°C, to obtain the photosensitive resin composition of each example. The content of surfactant (B) in Table 1 is the content relative to the total amount of the photosensitive resin composition. That is, the unit (ppm) of the content of surfactant (B) in Table 1 represents the content (mg) of surfactant (B) when the total amount of the photosensitive resin composition including the solvent is 1 kg, i.e., mg / kg.

[0149] (Preparation of cured film 1) The photosensitive resin composition of each example was applied to an 8-inch silicon wafer (manufactured by Advantec Co., Ltd.) using a spin coater, and then prebaked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. Next, the obtained coating film was irradiated with i-rays at a dose of 500 mJ / cm using an exposure device (manufactured by Nikon Corporation, product name: NSR-2005i) through a mask with a line and space pattern of 25 μm in width. 2 The exposed coating film was then developed with an alkaline developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 23°C for 100 seconds, rinsed with pure water for 60 seconds, and then cured in an oven at 230°C for 90 minutes to obtain cured film 1 having openings with a width of 25 μm.

[0150] (Preparation of cured film 2) The photosensitive resin composition of each example was applied to an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film was then cured in an oven at 230°C for 90 minutes to obtain cured film 2.

[0151] (Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis) As described above, the photosensitive resin composition of each example was used to prepare a cured film 1 having openings and a cured film 2 having no openings. The surface of the obtained cured film was subjected to TOF-SIMS analysis using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) TRIFT IV (manufactured by Physical Electronics). For cured film 1 having openings, the surface of the portion other than the openings was measured. The measurement conditions for each example are as follows. Analysis of the monomer and fragment structure of the molecules constituting the sample from the detection tendency of the mass spectrum revealed that in Examples 1 to 4, the peaks derived from polyether-modified polydimethylsiloxane 1 were C3H9Si + In Example 5, a peak (mass-to-charge ratio: 73) was detected as a peak derived from fluorine-based surfactant 1, F - A peak (mass-to-charge ratio: 19) was detected. Table 1 shows the measured peak intensities of the peaks derived from the surfactants of each example and the peak intensity ratios calculated from the measured values. (Measurement conditions) Ion species: Bi 3++ Acceleration voltage: 30 kV Detection depth: 1nm Analysis range: 100 μm square ·Measurement secondary ions: positive and negative (Measurement method) Bi 3++ Ion irradiation was performed, and secondary ions emitted from the outermost surface of the cured film (about 1 nm deep) were detected. The monomer and fragment structures of the molecules that make up the cured film were analyzed based on the detection trends in the mass spectrum.

[0152] (Evaluation of flux wettability) The photosensitive resin composition of each example was applied to an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 115°C for 430 seconds to obtain a coating film with a thickness of 8 µm. The obtained coating film was then cured in an oven at 220°C for 4 hours to obtain a cured film without openings. On the surface of the resulting cured film, 8 strips of 400 μm flux (Sparkle Flux WF-6317, manufactured by Senju Metal Industry Co., Ltd.) were applied at 1 mm intervals, 30 strips in a horizontal pattern, and the film was then reflowed at 260°C for 30 seconds. The flux wettability was evaluated visually according to the following criteria. The results are shown in Table 1. (Evaluation criteria) A: The flux barely spread and the droplets remained in their original shape. B: The flux spread somewhat, but the shape of the droplet did not change significantly and it did not mix with adjacent droplets. C: The flux spread widely enough to mix with neighboring droplets.

[0153] [Table 1]

Claims

1. A photosensitive resin composition comprising an alkali-soluble resin (A), a surfactant (B), and a photosensitizer (C), A photosensitive resin composition in which, when a surface of a cured film having an opening with a width of 25 μm, produced by the following method 1, is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), a peak derived from the surfactant (B) is detected on the cured film. (Method 1) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 µm. Next, the obtained coating film is irradiated with i-rays at a dose of 500 mJ / cm through a mask with a line and space pattern having a width of 25 µm. ２ The exposed coating film is then developed with an alkaline developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 23°C for 100 seconds, rinsed with pure water for 60 seconds, and then cured in an oven at 230°C for 90 minutes to obtain a cured film having openings with a width of 25 µm.

2. The peak intensity (X １ ) and the peak intensity (X ２ ) and the ratio (X １ / X ２ 2. The photosensitive resin composition according to claim 1, wherein the value of (a) is 0.01 or more and 0.30 or less. (Method 2) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film.

3. 3. The photosensitive resin composition according to claim 1, wherein the surfactant (B) comprises one or more surfactants selected from the group consisting of silicon-based surfactants (B1) and fluorine-based surfactants (B2).

4. The photosensitive resin composition according to claim 3 , wherein the silicone surfactant (B1) comprises a polyether-modified polydimethylsiloxane (b).

5. When the surface of the cured film prepared by the method 1 was subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), C derived from the polyether-modified polydimethylsiloxane (b) was detected. ３ H ９ Si ＋ The peak is detected, Within 1 nm from the surface of the cured film in the depth direction, C ３ H ９ Si ＋ The peak intensity (X １ 5. The photosensitive resin composition according to claim 4, wherein the molecular weight (Mn) is 50 or more and 1,100 or less.

6. When time-of-flight secondary ion mass spectrometry (TOF-SIMS) was performed on the surface of the cured film prepared by the following method 2, C derived from the polyether-modified polydimethylsiloxane (b) was detected. ３ H ９ Si ＋ The peak is detected, Within 1 nm from the surface of the cured film in the depth direction, C ３ H ９ Si ＋ The peak intensity (X ２ 5. The photosensitive resin composition according to claim 4, wherein the molecular weight (Mw) is 3,500 or more and 15,000 or less. (Method 2) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film.

7. When the surface of the cured film prepared by the method 1 was subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), F derived from the fluorine-based surfactant (B2) was － The peak is detected, F within 1 nm in the depth direction from the surface of the cured film － The peak intensity (X １ 4. The photosensitive resin composition according to claim 3, wherein the molecular weight (Mw) is 5,000 or more and 500,000 or less.

8. When time-of-flight secondary ion mass spectrometry (TOF-SIMS) was performed on the surface of the cured film prepared by the following method 2, F derived from the fluorine-based surfactant (B2) was detected. － The peak is detected, F within 1 nm in the depth direction from the surface of the cured film － The peak intensity (X ２ 4. The photosensitive resin composition according to claim 3, wherein the molecular weight (Mw) is 100,000 or more and 500,000 or less. (Method 2) The photosensitive resin composition is applied to an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The obtained coating film is then cured in an oven at 230°C for 90 minutes to obtain a cured film.

9. 5. The photosensitive resin composition according to claim 4, wherein the polyether-modified polydimethylsiloxane (b) has a weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography, of 1,000 or more and 5,000 or less.

10. 5. The photosensitive resin composition according to claim 4, wherein the polyether-modified polydimethylsiloxane (b) has a ratio (Mw / Mn) of the weight average molecular weight (Mw) in terms of polystyrene to the number average molecular weight (Mn) of 1 or more and 10 or less, as measured by gel permeation chromatography.

11. 5. The photosensitive resin composition according to claim 4, wherein the polyether-modified polydimethylsiloxane (b) has a weight average molecular weight of 1,000 or more and 5,000 or less at a maximum peak in a molecular weight distribution in terms of polystyrene, as measured by gel permeation chromatography.

12. The photosensitive resin composition according to claim 4 , wherein the polyether-modified polydimethylsiloxane (b) comprises a polyether-modified polydimethylsiloxane represented by the following general formula (1): 【Chemistry 1】 (In the general formula (1), m is an average value of 1 or more and 5 or less, p is an average value of 1 or more and 10 or less, q is an average value of 0 or more and less than 1, and R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)

13. 13. The photosensitive resin composition according to claim 12, wherein, in the general formula (1), x has an average value of 1 or more and 50 or less, and y has an average value of 1 or more and 10 or less.

14. The photosensitive resin composition according to claim 12, wherein x / y in the general formula (1) is 1 or more and 5 or less.

15. 3. The photosensitive resin composition according to claim 1, wherein the content of the surfactant (B) in the photosensitive resin composition is 130 ppm or more and 3000 ppm or less, based on the total amount of the photosensitive resin composition.

16. 3. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) has a weight average molecular weight (Mw) of 5,000 or more and 70,000 or less in terms of polystyrene, as measured by gel permeation chromatography.

17. 3. The photosensitive resin composition according to claim 1, wherein a content of the alkali-soluble resin (A) in the photosensitive resin composition is 30 parts by mass or more and 95 parts by mass or less, relative to 100 parts by mass of a total solid content of the photosensitive resin composition.

18. The photosensitive resin composition according to claim 1 or 2, further comprising a solvent (D).

19. The photosensitive resin composition according to claim 18, wherein the solvent (D) comprises one or more selected from the group consisting of γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, propylene glycol monomethyl ether, 3-methyl-2-oxazolidinone, 3-methoxy-N,N-dimethylpropanamide, and propylene glycol monomethyl ether acetate.

20. A cured film comprising a cured product of the photosensitive resin composition according to claim 1 or 2.

21. An electronic device comprising the cured film of claim 20.

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