Component, method for producing component, photosensitive resin composition, and semiconductor component

Abstract

Provided are: a member having a base material, insulating patterns disposed on the base material, and conductive patterns present between the insulating patterns; a method for manufacturing the member; a photosensitive resin composition used in the method for manufacturing the member; and a semiconductor member including the member. The difference between the maximum value and the minimum value of the distance from the surface of the base material to the surface of the conductive pattern on the opposite side from the base material in the direction perpendicular to the surface of the base material is 500 nm or less, and the angle formed by the bottom surface of the conductive pattern and the side surface of the conductive pattern is more than 90 DEG and 110 DEG or less.

Description

Technical Field

[0001] The present invention relates to a component, a method for manufacturing the component, a photosensitive resin composition, and a semiconductor component. Background Art

[0002] Electronic devices such as mobile phones and tablet computers are becoming increasingly smaller and more versatile. To meet this demand, the electronic circuits incorporated into these devices are being required to be even smaller, more highly integrated, and have higher-density packaging. This is driving demand for advancements in multilayer wiring technology.

[0003] In the process of manufacturing components having wiring formed therein by multilayer wiring technology, a SAP (SemiAdditive Process) method, a damascene method, and the like have been conventionally used.

[0004] The SAP method is a method in which a resist is formed in advance on a non-circuit portion, and after forming a circuit portion by electroplating, the resist is removed to form wiring, and then the spaces between the wirings are filled with an insulating member.

[0005] The damascene method is a method of forming wiring-shaped trenches in an interlayer insulating film and embedding metals such as copper. The damascene method has the advantage that even metals that are difficult to dry-etch, such as copper, can be easily used as wiring materials.

[0006] As the damascene method, two methods, a single damascene method and a double damascene method, are known.

[0007] Single damascene is a method in which, for example, copper wiring is embedded in an insulating film having vias and polished, an insulating film having wiring grooves is formed, copper wiring is embedded in the wiring grooves, and polished, forming separate via hole patterns and wiring patterns.

[0008] In contrast, dual damascene is a method in which an insulating film having wiring trenches and vias is formed, wiring metal is deposited to simultaneously fill the wiring trenches and vias, and then polished to form wiring.

[0009] In the damascene method, since the wiring metal is polished, a flat wiring structure can be obtained even without performing interlayer planarization, and thus it has the advantage of easily achieving multilayer fine wiring.

[0010] In particular, dual damascene technology has attracted attention as a technology capable of reducing manufacturing costs because it can shorten the number of manufacturing steps.

[0011] For example, Patent Document 1 describes a negative photosensitive resin composition and a method for manufacturing a semiconductor device component using the composition. The negative photosensitive resin composition includes a polyimide or a polyimide precursor, a compound that generates an acid when irradiated with activating light, and a cross-linking agent that acts through the acid, wherein the cross-linking agent includes at least one of a first compound and a second compound, the first compound having two or more functional groups selected from the group consisting of a hydroxymethyl group and an alkoxyalkyl group, and the second compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, and a glycidyloxy group.

[0012] Non-Patent Document 1 describes that a copper wiring layer is formed by a dual damascene process using a negative-type thermosetting phenolic material.

[0013] Previous technical literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Application Publication No. 2019-090946

[0016] Non-patent literature

[0017] Non-patent document 1: Advances in Photosensitive Polymer Based Damascene RDLProcesses: Toward Submicrometer Pitches With More Metal Layers, 2021 IEEE 71st Electronic Components and Technology Conference (ECTC), pp340-346 Summary of the Invention

[0018] Technical issues to be solved by the invention

[0019] In a method for manufacturing a component having a conductive pattern (wiring) formed thereon, it is required to improve the adhesiveness of the conductive pattern in order to suppress the occurrence of peeling of the conductive pattern.

[0020] An object of the present invention is to provide a component in which peeling of a conductive pattern is suppressed, a method for producing the component, a photosensitive resin composition used in the method for producing the component, and a semiconductor component including the component.

[0021] Means for solving technical problems

[0022] Hereinafter, examples of specific embodiments of the present invention will be described.

[0023] <1> A component having:

[0024] substrate;

[0025] an insulating pattern disposed on the substrate; and

[0026] The conductive pattern exists between the above-mentioned insulating pattern patterns,

[0027] The difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate in the direction perpendicular to the substrate surface is 500 nm or less,

[0028] An angle formed between the bottom surface of the conductive pattern and the side surface of the conductive pattern exceeds 90° and is equal to or less than 110°.

[0029] <2> like <1> In the component, the conductive pattern is a line and space pattern, and the line width of the conductive pattern is greater than or equal to 0.1 μm and less than or equal to 10 μm.

[0030] <3> like <1> or <2> The component, wherein the indentation elastic modulus of the insulating pattern is 6.0 GPa or less.

[0031] <4> like <1> to <3> The component described in any one of the preceding claims, wherein the insulating pattern comprises polyimide.

[0032] <5> like <4> The component, wherein the cyclization rate of the polyimide is above 70%.

[0033] <6> like <1> to <5> The component described in any one of the preceding claims, wherein the insulating pattern contains an ionic compound.

[0034] <7> A component comprising a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on at least a portion of the surface of the first insulating pattern, and a conductive pattern for conducting electricity between a region between the first insulating patterns and a region between the second insulating patterns.

[0035] The difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate in a direction perpendicular to the substrate surface is 500 nm or less,

[0036] An angle formed by a side surface of the conductive pattern in a region between the bottom surface of the conductive pattern and the second insulating pattern exceeds 90° and is equal to or less than 110°.

[0037] <8> A method for manufacturing a component, the component having:

[0038] substrate;

[0039] an insulating pattern disposed on the substrate; and

[0040] The conductive pattern exists between the above-mentioned insulating pattern patterns,

[0041] The manufacturing method of the above-mentioned component has the following features:

[0042] a conductive layer forming step of forming a conductive layer in regions between the insulating patterns of the substrate formed with the insulating patterns and on the insulating patterns to obtain component A;

[0043] a grinding step of grinding the component A to obtain a component with the conductive pattern and the insulating pattern exposed on the surface;

[0044] The angle formed by the bottom surface of the conductive pattern of the component and the side surface of the conductive pattern exceeds 90° and is equal to or less than 110°.

[0045] <9> like <8> The method for manufacturing the component, wherein:

[0046] Before the above conductive layer forming step,

[0047] A film forming process comprising the step of applying the insulating pattern forming composition to the substrate to form a film,

[0048] The insulating pattern forming composition includes at least one compound selected from the group consisting of a photoradical generator and a photoacid generator.

[0049] <10> like <9> The method for producing a component, wherein the i-ray transmittance of a 3 μm-thick film formed by heating the insulating pattern-forming composition at 100° C. for 3 minutes is 5% or more.

[0050] <11> like <9> or <10> The method for manufacturing a component according to any one of the preceding claims, wherein:

[0051] After the film forming step, the method includes: a drying step of drying the film; an exposure step of exposing the dried film; and a developing step of developing the exposed film with a developer.

[0052] The insulating pattern forming composition was applied on a silicon wafer and heated at 100°C for 180 seconds and then at 100 mJ / cm 2 The swelling rate of the film irradiated with i-rays at an irradiation dose of 1000 nm and heated at 110° C. for 3 minutes with respect to the above-mentioned developer was 15% by volume or less.

[0053] <12> like <9> to <11> The method for manufacturing a component according to any one of the preceding claims, wherein:

[0054] After the film forming step, a heating step of heating the film at two or more heating temperatures is included.

[0055] <13> A method for manufacturing a component, the component comprising a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on at least a portion of the surface of the first insulating pattern, and a conductive pattern for conducting between an area between the first insulating pattern and an area between the second insulating pattern.

[0056] The manufacturing method of the above-mentioned component includes steps A to C.

[0057] The angle formed by the bottom surface of the conductive pattern of the component and the side surface of the conductive pattern exceeds 90° and is equal to or less than 110°.

[0058] Step A: Preparing a component A including the first insulating pattern and the second insulating pattern

[0059] Step B: forming a conductive layer on the area between the first insulating patterns, the area between the second insulating patterns, and the second insulating patterns of the component A to obtain a conductive layer forming step of component B

[0060] Step C: Polishing the component B to obtain a component where the conductive pattern and the second insulating pattern are exposed.

[0061] <14> A photosensitive resin composition for <8> to <12> The formation of the insulating pattern in any one of the manufacturing methods.

[0062] <15> like <14> The photosensitive resin composition comprises polyimide or a polyimide precursor.

[0063] <16> A semiconductor component comprising <1> to <7> Any one of the components described above.

[0064] Effects of the Invention

[0065] According to the present invention, there are provided a component in which peeling of a conductive pattern is suppressed, a method for producing the component, a photosensitive resin composition used in the method for producing the component, and a semiconductor component including the component. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a schematic cross-sectional view showing an example of the first member of the present invention.

[0067] Figure 2 This is a schematic cross-sectional view showing an example of a case where a conductive pattern is deformed.

[0068] Figure 3This is a schematic cross-sectional view showing an example of the second member of the present invention.

[0069] Figure 4 It is a process explanatory diagram schematically showing the steps of the method for manufacturing the first component according to one embodiment of the present invention using cross-sectional views.

[0070] Figure 5 It is a process explanatory diagram schematically showing (part of) the process of the manufacturing method of the second member according to one embodiment of the present invention using a cross-sectional view.

[0071] Figure 6 This is a process explanation diagram schematically showing (part of) the process of the method for manufacturing the second component according to one embodiment of the present invention in cross-sectional view (continued) Figure 5 ). DETAILED DESCRIPTION

[0072] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0073] In this specification, the numerical range expressed by the symbol “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit, respectively.

[0074] In this specification, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0075] In the description of groups (atomic groups), the term "unsubstituted" or "unsubstituted" includes groups (atomic groups) without substitution as well as groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0076] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation.

[0077] In this specification, “(meth)acrylate” means both or either of “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either of “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either of “acryloyl” and “methacryloyl”.

[0078] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0079] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, the solid content concentration in this specification refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0080] In this specification, as long as there is no special instructions, weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, about weight average molecular weight (Mw) and number average molecular weight (Mn), for example, can be obtained by using HLC-8220GPC (TOSOH CORPORATION system), and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgelSuper HZ2000 (more than TOSOH CORPORATION system) are connected in series and used as column. As long as there is no special instructions, these molecular weights are measured using THF (tetrahydrofuran) as eluent. Wherein, when solubility is low, THF is not suitable as eluent, and NMP (N- methyl -2- pyrrolidone) can also be used. Furthermore, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254 nm was used for detection in GPC measurement.

[0081] In this specification, about the positional relationship of each layer constituting laminated body, when being recorded as " on " or " down ", as long as there are other layers on the upper side or lower side of the layer becoming a benchmark in the multiple layers concerned. That is, the 3rd layer or the 3rd element can be further sandwiched between the layer becoming a benchmark and the above-mentioned other layers, and the layer becoming a benchmark and the above-mentioned other layers do not need to contact. Unless otherwise specified, the direction of the substrate stacked layer will be referred to as " on ", or, when there is a resin composition layer, the direction from the substrate toward the resin composition layer will be referred to as " on ", and its opposite direction will be referred to as " down ". In addition, the setting of these up and down directions is for the convenience in this specification, and in actual mode, the " up " direction in this specification can also be different from the vertical direction.

[0082] In this specification, unless otherwise specified, each component contained in a composition may include two or more compounds belonging to the component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to the component.

[0083] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0084] In this specification, a combination of preferred embodiments is considered a more preferred embodiment.

[0085] (part)

[0086] A component of the first embodiment of the present invention (hereinafter also referred to as the "first component") comprises: a substrate; an insulating pattern arranged on the above-mentioned substrate; and a conductive pattern existing between the patterns of the above-mentioned insulating pattern, wherein the difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side of the substrate in a direction perpendicular to the above-mentioned substrate surface is less than 500 nm, and the angle formed by the bottom surface of the above-mentioned conductive pattern and the side surface of the above-mentioned conductive pattern exceeds 90° and is less than 110°.

[0087] A component of the second embodiment of the present invention (hereinafter also referred to as the "second component") comprises a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on the surface of at least a portion of the first insulating pattern, and a conductive pattern that conducts (electrically conducts) an area between the first insulating pattern and an area between the second insulating pattern, wherein the difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side of the substrate in the direction perpendicular to the substrate surface is less than 500 nm, and the angle formed by the bottom surface of the conductive pattern and the side surface of the conductive pattern in the area between the patterns of the second insulating pattern exceeds 90° and is less than 110°.

[0088] In order to reduce the difference between the maximum value and the minimum value to 500 nm or less, it is necessary to polish the surface of the component.

[0089] Here, when the angle exceeds 90°, stress is less likely to be applied to the lower end of the conductive pattern when the surface of the component is polished, thereby suppressing peeling of the conductive pattern.

[0090] Furthermore, by setting the angle to be 110° or less, a fine pattern can be formed.

[0091] Furthermore, when the angle exceeds 90° during polishing, the total area of the insulating pattern exposed on the polished surface is reduced compared to when the angle is less than 90°. As a result, the amount of polishing debris generated from the insulating pattern during polishing is reduced, and scratches on the polished surface of the component are suppressed.

[0092] Neither Patent Document 1 nor Non-Patent Document 1 describes nor suggests that the angle formed between the bottom surface of the conductive pattern and the side surface of the conductive pattern exceeds 90° and is 110° or less.

[0093] Hereinafter, the first component of the present invention will be described in detail.

[0094] <Part 1>

[0095] A first component of the present invention includes a substrate, an insulating pattern disposed on the substrate, and a conductive pattern present between the insulating patterns.

[0096] 〔Base material〕

[0097] The substrate is not particularly limited and may include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramics, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe; paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; and electrode plates for plasma display panels (PDPs). The substrate may also have a bonding layer or an oxide layer based on hexamethyldisilazane (HMDS) or a sealing material (epoxy molding compound: EMC) on its surface.

[0098] The substrate may be in the form of a wafer or a panel.

[0099] Particularly, in the present invention, a semiconductor manufacturing substrate is preferred, and a silicon substrate (silicon wafer) is more preferred.

[0100] The substrate may have an electronic circuit region including an electronic circuit. The electronic circuit may include elements such as semiconductors. Preferably, the electronic circuit is electrically connected to the conductive pattern.

[0101] 〔Insulation pattern〕

[0102] The insulating pattern preferably includes polyimide or polybenzoxazole, and more preferably includes polyimide.

[0103] The content of polyimide or polybenzoxazole (the total content when two or more types are included) is preferably 20 to 99.5 mass %, more preferably 30 to 99 mass %, further preferably 40 to 98 mass %, and particularly preferably 50 to 97 mass % relative to the total mass of the insulating pattern.

[0104] The cyclization rate (imidization rate) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the cyclization rate is not particularly limited, but may be 100% or less. The cyclization rate is measured by the method described below.

[0105] The insulating pattern is preferably a cured product of the photosensitive resin composition described below.

[0106] The insulating pattern may further have another layer formed between the insulating pattern and the substrate, and is preferably in contact with the substrate.

[0107] The insulating pattern is not particularly limited to a line and space pattern, a hole pattern, or the like, but is preferably a hole pattern.

[0108] When the insulating pattern is a line-and-space pattern, the interval between the lines (space width) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm.

[0109] When the insulating pattern is a hole pattern, the diameter of the bottom surface of the hole pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm. When the bottom surface of the hole pattern is not circular, the above diameter is calculated as the equivalent circle diameter. The equivalent circle diameter refers to the diameter of a circle having the same area as the bottom surface of the hole pattern.

[0110] The thickness of the insulating pattern is not particularly limited, but is preferably 100 nm or greater, more preferably 300 nm or greater, even more preferably 500 nm or greater, and even more preferably 1 μm or greater. The upper limit is not particularly limited, but is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be measured using a known film thickness measuring device.

[0111] In this specification, thickness refers to the length in a direction perpendicular to the surface of a substrate.

[0112] The indentation elastic modulus of the insulating pattern is not particularly limited, but is preferably 6.0 GPa or less, more preferably 4 to 6 GPa, and even more preferably 4.5 to 5.5 GPa. The indentation elastic modulus can be measured by a nanoindentation test.

[0113] The insulating pattern preferably includes an ionic compound.

[0114] The content of the ionic compound is preferably 0.001 to 5 mass %, more preferably 0.01 to 3 mass %, and even more preferably 1 to 2 mass % relative to the total mass of the insulating pattern.

[0115] Examples of the ionic compound include photoacid generators and base generators described below.

[0116] The details of these compounds are described in the description of the photosensitive resin composition to be described later.

[0117] 〔Conductive pattern〕

[0118] The conductive pattern exists between the patterns of the insulating pattern.

[0119] The conductive pattern is preferably a conductive pattern that fills the area between the insulating patterns. Filling means filling the area between the patterns to prevent the generation of empty spaces between the patterns. Other layers such as a seed layer may exist in the area between the patterns.

[0120] The conductive pattern preferably includes at least one metal selected from the group consisting of tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), palladium (Pd), platinum (Pt), cobalt (Co), nickel (Ni), zinc (Zn), ruthenium (Ru), iridium (Ir), rhodium (Rh), lead (Pb), bismuth (Bi) and indium (In), and includes at least one metal selected from the group consisting of copper, tin and nickel, and more preferably includes copper. In this specification, at least one of the alloys containing metal X or containing the metal thereof is collectively referred to and simply described as "containing metal X". In addition, the alloy may contain elements other than those exemplified above. For example, a copper alloy may contain silicon atoms to form a Casson alloy. In addition, there may be inevitably dissolved oxygen or organic residues of the raw material compound mixed during precipitation.

[0121] The conductive pattern may be a wiring terminal composed of a plurality of different components.

[0122] Among these, the conductive pattern is preferably a pattern composed of copper.

[0123] The conductive pattern is preferably a line and space pattern.

[0124] Furthermore, the conductive pattern is a line and space pattern, and the line width of the conductive pattern is preferably 0.1 μm or more and 10 μm or less, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 3 μm.

[0125] The conductive pattern may be in contact with the insulating pattern, or a seed layer or the like may be further included between the conductive pattern and the insulating pattern.

[0126] [Seed layer]

[0127] The first member of the present invention may further include a seed layer (a feed layer for electrolytic copper plating).

[0128] A seed layer preferably exists between the insulating pattern and the conductive pattern.

[0129] Examples of the seed layer include a layer made of metal such as titanium, chromium, and nickel.

[0130] 〔Barrier layer〕

[0131] The first member of the present invention may further include a barrier layer.

[0132] The barrier layer is preferably present on the surface of the conductive pattern on the side opposite to the substrate.

[0133] Examples of the barrier layer include a layer made of a metal such as nickel.

[0134] [Distance from the substrate surface to the surface of the conductive pattern opposite to the substrate]

[0135] In the first member of the present invention, the difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern opposite to the substrate in a direction perpendicular to the substrate surface is 500 nm or less.

[0136] The difference between the maximum value and the minimum value is preferably 400 nm or less, more preferably 300 nm or less.

[0137] Figure 1 This is a schematic cross-sectional view showing an example of the first member of the present invention.

[0138] exist Figure 1 In the embodiment, insulating patterns 102 are formed on a substrate 100 , and a seed layer 104 and a conductive pattern 106 are formed in regions between the insulating patterns 102 .

[0139] Here, h1, h2, and h3 are examples of distances from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate.

[0140] The difference between the minimum value and the maximum value of the distances h1, h2, h3, etc. from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate is 500 nm or less.

[0141] 〔1st pattern angle〕

[0142] In the first component of the present invention, the angle formed by the bottom surface of the conductive pattern and the side surface of the conductive pattern (also referred to as "first pattern angle") exceeds 90° and is 110° or less.

[0143] The first pattern angle is preferably greater than 90° and less than 105°, and more preferably greater than 90° and less than 100°.

[0144] exist Figure 1 In FIG. 1 , the angle θ is an example of the first pattern angle.

[0145] In the present invention, at least one first pattern angle is sufficient to be greater than 90° and less than 110°, and preferably the average value of all first pattern angles is greater than 90° and less than 110°. Furthermore, it is also a preferred embodiment of the present invention that all first pattern angles are greater than 90° and less than 110°.

[0146] Here, when the side wall of the conductive pattern has deformation, the angle formed by the straight line connecting the end point of the bottom surface of the conductive pattern and the end point of the exposed portion of the conductive pattern on the side opposite to the substrate and the bottom surface of the conductive pattern is set as the first pattern angle.

[0147] Figure 2 This is a schematic cross-sectional view showing an example of a case where a conductive pattern is deformed.

[0148] exist Figure 2 In FIG, an angle θ formed between an imaginary line connecting an end point b of the bottom surface of the conductive pattern and an end point a of the exposed portion of the conductive pattern on the side opposite to the substrate and the bottom surface of the conductive pattern is a first pattern angle.

[0149] The first pattern angle can be adjusted by setting the composition of the insulating pattern forming composition described later (resin type, physical properties of the polymerizable compound), exposure conditions such as exposure amount, exposure time, and focus position in the exposure process, and developer in the development process.

[0150] <Part 2>

[0151] The second component of the present invention comprises a substrate, a first insulating pattern present on the above-mentioned substrate, a second insulating pattern present on the surface of at least a portion of the above-mentioned first insulating pattern, and a conductive pattern that conducts the area between the above-mentioned first insulating pattern and the area between the above-mentioned second insulating pattern, wherein the difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side of the substrate in the direction perpendicular to the substrate surface is less than 500 nm, and the angle formed by the side surface of the above-mentioned conductive pattern in the area between the bottom surface of the above-mentioned conductive pattern and the pattern of the above-mentioned second insulating pattern exceeds 90° and is less than 110°.

[0152] 〔Base material〕

[0153] As the base material of the second member, the same base material as the base material of the first member described above can be used, and the preferred aspects are also the same.

[0154] [First insulation pattern]

[0155] The first insulating pattern preferably includes polyimide or polybenzoxazole, and more preferably includes polyimide.

[0156] The content of polyimide or polybenzoxazole (the total content when two or more types are included) relative to the total mass of the first insulating pattern is preferably 20 to 99.5 mass %, more preferably 30 to 99 mass %, further preferably 40 to 98 mass %, and particularly preferably 50 to 97 mass %.

[0157] The cyclization rate (imidization rate) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the cyclization rate is not particularly limited, but may be 100% or less. The cyclization rate is measured by the method described below.

[0158] The insulating pattern is preferably a cured product of the photosensitive resin composition described below.

[0159] The first insulating pattern is preferably a cured product of a first insulating pattern forming composition described below.

[0160] Furthermore, the first insulating pattern may further have another layer formed between the pattern and the substrate, and is preferably in contact with the substrate.

[0161] The first insulating pattern is not particularly limited to a line and space pattern, a hole pattern, or the like, but is preferably a hole pattern.

[0162] When the first insulating pattern is a line-and-space pattern, the interval between the lines (space width) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm.

[0163] When the first insulating pattern is a hole pattern, the diameter of the bottom surface of the hole pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm. When the bottom surface of the hole pattern is not circular, the above diameter is calculated as the equivalent circle diameter. The equivalent circle diameter refers to the diameter of a circle having the same area as the bottom surface of the hole pattern.

[0164] The thickness of the first insulating pattern is not particularly limited, but is preferably 100 nm or greater, more preferably 300 nm or greater, even more preferably 500 nm or greater, and even more preferably 1 μm or greater. The upper limit is not particularly limited, but is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be measured using a known film thickness measuring device.

[0165] The indentation elastic modulus of the first insulating pattern is not particularly limited, but is preferably 6.0 GPa or less, more preferably 4.0 to 6.0 GPa, and even more preferably 4.5 to 5.5 GPa. The indentation elastic modulus can be measured by nanoindentation.

[0166] [Second insulation pattern]

[0167] The second insulating pattern preferably includes polyimide or polybenzoxazole, and more preferably includes polyimide.

[0168] The content of polyimide or polybenzoxazole (the total content of these when two or more types are included) relative to the total mass of the second insulating pattern is preferably 20 to 99.5 mass %, more preferably 30 to 99 mass %, further preferably 40 to 98 mass %, and particularly preferably 50 to 97 mass %.

[0169] The cyclization rate (imidization rate) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the cyclization rate is not particularly limited, but may be 100% or less. The cyclization rate is measured by the method described below.

[0170] The insulating pattern is preferably a cured product of the photosensitive resin composition described below.

[0171] The second insulating pattern is preferably a cured product of a second insulating pattern forming composition described later.

[0172] Furthermore, the second insulating pattern may have another layer formed between the second insulating pattern and the first insulating pattern, and is preferably in contact with the first insulating pattern.

[0173] It is preferable that the first insulating pattern and the second insulating pattern differ in at least a portion of their patterns in the substrate surface direction.

[0174] The second insulating pattern is not particularly limited to a line and space pattern, a hole pattern, or the like, but is preferably a line and space pattern.

[0175] When the second insulating pattern is a line-and-space pattern, the interval between the lines (space width) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 3 μm.

[0176] When the pattern formed in the second insulating pattern is a hole pattern, the diameter of the bottom surface of the hole pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm. When the bottom surface of the hole pattern is not circular, the above diameter is calculated as the equivalent circle diameter. The equivalent circle diameter refers to the diameter of a circle having the same area as the bottom surface of the hole pattern.

[0177] The thickness of the second insulating pattern is not particularly limited, but is preferably 100 nm or greater, more preferably 300 nm or greater, even more preferably 500 nm or greater, and even more preferably 1 μm or greater. The upper limit is not particularly limited, but is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be measured using a known film thickness measuring device.

[0178] The indentation elastic modulus of the second insulating pattern is not particularly limited, but is preferably 6.0 GPa or less, more preferably 4.0 to 6.0 GPa, and even more preferably 4.5 to 5.5 GPa.

[0179] 〔Conductive pattern〕

[0180] The conductive pattern provides electrical conduction between the region between the first insulating patterns and the region between the second insulating patterns.

[0181] The conductive pattern preferably fills the area between the first insulating patterns and the area between the second insulating patterns. Filling means filling the area between the patterns to prevent the formation of empty gaps between the patterns. Other layers such as a seed layer may exist in the area between the patterns.

[0182] Furthermore, the conductive pattern is divided into two conductive patterns: a conductive pattern filling a region between the first insulating patterns and a conductive pattern filling a region between the second insulating patterns, and these conductive patterns may be in electrical contact with each other.

[0183] Preferred aspects of the conductive pattern are the same as those of the conductive pattern of the first member described above.

[0184] The conductive pattern may be in contact with the first insulating pattern, or a seed layer or the like may be further included between the conductive pattern and the first insulating pattern.

[0185] The conductive pattern may be in contact with the second insulating pattern, and may further include a seed layer or the like between the conductive pattern and the second insulating pattern.

[0186] [Seed layer]

[0187] The second member of the present invention may further include a seed layer.

[0188] The seed layer is preferably present in at least one of between the first insulating pattern and the conductive pattern and between the second insulating pattern and the conductive pattern, and more preferably in both of them.

[0189] Preferred aspects of the seed layer are the same as those of the seed layer of the first member described above.

[0190] 〔Barrier layer〕

[0191] The second member of the present invention may further include a barrier layer.

[0192] The barrier layer is preferably present on the surface of the conductive pattern on the side opposite to the substrate.

[0193] Preferred aspects of the barrier layer are the same as those of the barrier layer of the first member described above.

[0194] [Distance from the substrate surface to the surface of the conductive pattern opposite to the substrate]

[0195] In the second member of the present invention, the difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern opposite to the substrate in a direction perpendicular to the substrate surface is 500 nm or less.

[0196] The difference between the maximum value and the minimum value is preferably 400 nm or less, more preferably 300 nm or less.

[0197] Figure 3 This is a schematic cross-sectional view showing an example of the second member of the present invention.

[0198] exist Figure 3 In (a), a substrate 100 is described in which an insulating pattern 114 and a conductive pattern 116 are formed on a silicon wafer 112. A first insulating pattern 122 is formed on the substrate 100, a second insulating pattern 124 is formed on the first insulating pattern 122, and a conductive pattern 126 and a seed layer 128 are formed in the region between the first insulating pattern 122 and the region between the second insulating pattern 124 to provide electrical connection between the first insulating pattern 122 and the second insulating pattern 124.

[0199] Here, h4, h5, and h6 are examples of distances from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate.

[0200] The difference between the minimum value and the maximum value of the distances h4, h5, h6, etc. from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate is 500 nm or less.

[0201] 〔2nd pattern angle〕

[0202] In the second component of the present invention, the angle formed by the bottom surface of the conductive pattern and the side surface of the conductive pattern (also referred to as "second pattern angle") exceeds 90° and is 110° or less.

[0203] The second pattern angle is preferably greater than 90° and less than 105°, and more preferably greater than 90° and less than 100°.

[0204] exist Figure 3 In (a), the angle θ is an example of the second pattern angle. θ is the angle formed by the bottom surface of the conductive pattern and the side surface of the conductive pattern. Figure 3 The dotted line in (a) is an extension line of the side surface of the conductive pattern, and the dotted chain line is an extension line of the bottom surface of the conductive pattern. The angle θ formed at the intersection of these is the second pattern angle.

[0205] Figure 3 (b) is correct Figure 3The conductive pattern shown on the far right of (a) is a diagram in which hatching of each component is deleted and boundaries of the component are marked in gray to make the dashed line, the dotted chain line, and θ easier to identify.

[0206] In the present invention, at least one second pattern angle may be greater than 90° and less than 110°, and the average value of all second pattern angles is preferably greater than 90° and less than 110°. Furthermore, it is also a preferred embodiment of the present invention that all second pattern angles are greater than 90° and less than 110°.

[0207] Here, when the sidewall of the conductive pattern has deformation, the angle formed by the end point of the bottom surface of the conductive pattern and the end point of the exposed portion of the conductive pattern on the side opposite to the substrate is defined as the second pattern angle, which is the same as the first pattern angle.

[0208] The second pattern angle can be adjusted by setting the composition of the second insulating pattern forming composition described later (resin type, physical properties of polymerizable compound), exposure conditions such as exposure amount, exposure time, focus position in the second exposure process, and the developer in the second development process.

[0209] (Method for manufacturing semiconductor component)

[0210] The semiconductor component of the present invention is a component including the first component or the second component of the present invention.

[0211] As semiconductor components, there are the following Figure 4 (c) or Figure 6 The semiconductor components described in (c) or semiconductor components in which one or more other components are mounted on these components, etc.

[0212] That is, the semiconductor component of the present invention may be a component in which another component (such as a semiconductor wafer) is further mounted on the first component or the second component.

[0213] Other semiconductor components include processors (CPUs), 1GHz-112GHz serial devices, logic, accelerators (IPUs, TPUs, etc.), graphics processing units (GPUs), volatile memories such as DRAM (Dynamic Random Access Memory) and SRAM (Static Random Access Memory), non-volatile memories such as flash memories, RF chips, silicon photonic chips, MEMS (Micro Electro Mechanical Systems), sensor chips, etc., and can be selected according to the intended use.

[0214] These semiconductor wafers are preferably electrically connected to the conductive patterns in the component.

[0215] (Method of manufacturing components)

[0216] <Method for Manufacturing the First Component>

[0217] The first embodiment of the present invention provides a method for manufacturing a component (also referred to as "a method for manufacturing the first component"), wherein the component comprises: a substrate; an insulating pattern arranged on the substrate; and a conductive pattern existing between the insulating patterns. The method for manufacturing the component comprises: a conductive layer forming step of forming a conductive layer in an area between the insulating patterns of the substrate on which the insulating pattern is formed and on the insulating pattern to obtain component A; and a grinding step of grinding the component A to obtain a component in which the conductive pattern and the insulating pattern are exposed on the surface, wherein the angle formed by the bottom surface of the conductive pattern of the component and the side surface of the conductive pattern exceeds 90° and is less than 110°.

[0218] According to the method for manufacturing a first component of the present invention, the above-mentioned first component of the present invention is manufactured.

[0219] That is, the angle (first pattern angle) between the substrate, insulating pattern, conductive pattern, and the bottom surface of the conductive pattern and the side surface of the conductive pattern in the manufactured component are as described above, and the preferred embodiments of these are also the same as those in the above-mentioned first component.

[0220] Furthermore, in the method for manufacturing the first component of the present invention, prior to the conductive layer forming step, it is preferred to have a film forming step including the step of applying an insulating pattern forming composition (hereinafter also referred to as "resin composition") on the above-mentioned substrate to form a film.

[0221] Furthermore, the method for manufacturing the first component of the present invention preferably includes, after the film forming step, a drying step of drying the film, an exposure step of exposing the dried film, and a development step of developing the exposed film using a developer.

[0222] Furthermore, the method for manufacturing the first member of the present invention preferably includes a heating step after the film forming step.

[0223] <Film Formation Step>

[0224] The method for producing the first component of the present invention preferably includes a film forming step comprising applying an insulating pattern forming composition (hereinafter also referred to as "resin composition") to form a film on the substrate before the conductive layer forming step.

[0225] In particular, the method for manufacturing the first component of the present invention preferably includes, before the conductive layer forming step, a film forming step comprising applying an insulating pattern forming composition to the substrate to form a film, wherein the insulating pattern forming composition comprises at least one compound selected from the group consisting of a photoradical generator and a photoacid generator. Details of these components will be described later.

[0226] The i-ray transmittance of a 3 μm-thick film formed by heating the insulating pattern forming composition at 100° C. for 3 minutes is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more.

[0227] The composition of the insulating pattern forming composition will be described in detail later.

[0228] As a method of applying the resin composition to a substrate, coating is preferred.

[0229] As the method applied, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet method etc. can be cited. From the viewpoint of uniformity of film thickness, preferably spin coating, slit coating, spray coating or inkjet method, from the viewpoint of uniformity of film thickness and the viewpoint of productivity, more preferably spin coating and slit coating method. According to the method applied, the solid content concentration or coating conditions of the resin composition are adjusted, thereby a film of desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, preferably spin coating or spray coating, inkjet method etc., if it is a rectangular substrate, preferably slit coating, spray coating, inkjet method etc. In the case of spin coating, for example, it is possible to apply for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.

[0230] Furthermore, a method of transferring a coating film formed on a temporary support body in advance by the above-mentioned applying method to a substrate can also be applied.

[0231] As the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

[0232] Furthermore, a process of removing excess film from the edge of the substrate may be performed. Examples of such a process include edge bead rinse (EBR) and backwash.

[0233] A pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0234] <Drying Process>

[0235] After the film forming step (layer forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent.

[0236] That is, the method for manufacturing the first member of the present invention may include a drying step of drying the film formed in the film forming step.

[0237] The drying step is preferably performed after the film forming step and before the exposure step.

[0238] The film drying temperature in the drying step is preferably 50°C to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Drying can also be performed under reduced pressure. The drying time can be, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0239] <Exposure Process>

[0240] The film can be subjected to an exposure step of selectively exposing the film.

[0241] Selective exposure refers to exposing a portion of a film to light, and selective exposure forms exposed regions (exposed portions) and unexposed regions (non-exposed portions) on the film.

[0242] The exposure dose is not particularly limited as long as the resin composition of the present invention can be cured. For example, it is preferably 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0243] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0244] When describing the exposure wavelength in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, and 355 nm), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beams, and (7) second harmonics of YAG lasers at 532 nm and third harmonics at 355 nm. Exposure using a high-pressure mercury lamp is particularly preferred, and exposure using i-rays is more preferred from the perspective of exposure sensitivity.

[0245] The exposure method is not particularly limited as long as at least a portion of the film composed of the resin composition of the present invention is exposed. Examples of the exposure method include exposure using a photomask and exposure by laser direct imaging.

[0246] <Post-exposure heating process>

[0247] The film may be subjected to a step of heating after exposure (post-exposure heating step).

[0248] That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

[0249] The post-exposure heating step can be performed after the exposure step and before the development step.

[0250] The heating temperature in the post-exposure heating step is preferably 50°C to 160°C, more preferably 60°C to 120°C.

[0251] The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0252] The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the temperature at the start of heating to the maximum heating temperature.

[0253] Furthermore, the heating rate can be appropriately changed during the heating process.

[0254] The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

[0255] Furthermore, during heating, it is preferable to conduct the heating in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0256] <Development Process>

[0257] The film after exposure can be subjected to a development step of developing with a developer to form a pattern.

[0258] That is, the method for producing the first member of the present invention may include a developing step of developing the film exposed in the exposure step using a developing solution to form a pattern.

[0259] By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.

[0260] Here, development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and development in which the exposed portion of the film is removed by the development step is referred to as positive development.

[0261] 〔Developer〕

[0262] As a developer used in the development step, a developer containing an alkaline aqueous solution or an organic solvent can be mentioned.

[0263] When the developer is an alkaline aqueous solution, examples of the alkaline compound that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0264] When the developer contains an organic solvent, the compounds described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. Furthermore, preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Preferred examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0265] Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, more preferably containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and particularly preferably containing cyclopentanone.

[0266] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. The above content may also be 100% by mass.

[0267] When the developer does not contain an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. The at least one of the alkaline compound and the alkali generator in the developer may penetrate into the pattern, thereby sometimes improving properties such as elongation at break of the pattern.

[0268] As the basic compound, an organic base is preferred from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated).

[0269] As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. In order to promote the imidization reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are further preferred, and tertiary amines are particularly preferred.

[0270] As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, a compound that is unlikely to remain in the cured film (the obtained cured product) is preferred. From the viewpoint of promoting cyclization, a compound whose residual amount is unlikely to be reduced by vaporization or the like before heating is preferred.

[0271] Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and further preferably 100°C to 230°C at normal pressure (101, 325 Pa).

[0272] The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[0273] For example, when the boiling point of the organic solvent is 100°C, the base used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.

[0274] The developer may contain only one basic compound or two or more basic compounds.

[0275] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butylenediamine, 1,5-diaminopentane, and N-methylhexylamine. , N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, etc.

[0276] Preferred embodiments of the base generator are the same as those of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

[0277] When the developer contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.

[0278] When the basic compound or base generator is solid in an environment where a developer is used, the content of the basic compound or base generator is preferably 70 to 100% by mass relative to the total solid content of the developer.

[0279] The developer may contain only one or more of the alkaline compound and the alkali generator. When the alkaline compound and the alkali generator are two or more, the total amount thereof is preferably within the above range.

[0280] The developer may further contain other components.

[0281] Examples of other components include known surfactants and known defoaming agents.

[0282] [Developer Supply Method]

[0283] The method for supplying the developer is not particularly limited as long as the desired pattern can be formed. Examples include immersing the film-formed substrate in the developer, using a nozzle to supply the developer to the film formed on the substrate using a rotary immersion development method, and continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

[0284] From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a straight nozzle or continuously supply it using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply it using a spray nozzle.

[0285] In addition, the following process can be adopted: after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a straight nozzle again, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times.

[0286] Examples of methods for supplying the developer in the development step include continuously supplying the developer to the substrate, maintaining the developer substantially stationary on the substrate, vibrating the developer on the substrate using ultrasound or the like, and combinations thereof.

[0287] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0288] In the development process, the pattern may be cleaned (rinsed) using a rinse solution after being treated with a developer. Alternatively, a method may be employed in which a rinse solution is supplied before the developer in contact with the pattern is completely dried.

[0289] Here, the insulating pattern forming composition was applied on a silicon wafer and heated at 100° C. for 180 seconds and then irradiated with 100 mJ / cm 2 The swelling ratio of the film irradiated with i-rays at an irradiation dose of 1000 nm and heated at 110° C. for 3 minutes with respect to the above-mentioned developer is preferably 15% by volume or less, more preferably 12% by volume or less, and further preferably 10% by volume or less.

[0290] [Rinse solution]

[0291] When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse liquid. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0292] Examples of the organic solvent in the case where the rinse solution contains an organic solvent include the same organic solvents as exemplified in the case where the developer contains an organic solvent.

[0293] The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility in the pattern than the organic solvent contained in the developer.

[0294] When the rinse liquid contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0295] When the rinsing liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more relative to the total mass of the rinsing liquid. Furthermore, the organic solvent may be 100% by mass relative to the total mass of the rinsing liquid.

[0296] The flushing liquid may contain at least one of a basic compound and an alkali generator.

[0297] Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains at least one of an organic solvent, an alkaline compound, and an alkali generator is also one of the preferred embodiments of the present invention.

[0298] Examples of the alkaline compound and the alkaline generator contained in the rinse solution include the alkaline compounds and the compounds exemplified as the alkaline generators that may be contained in the developer containing an organic solvent, and preferred embodiments are also the same.

[0299] The basic compound and base generator contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.

[0300] When the rinse liquid contains at least one of a basic compound and an alkali generator, the content of the basic compound or alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.

[0301] When the basic compound or base generator is solid in the environment where the rinse liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass relative to the total solid content of the rinse liquid.

[0302] When the rinse liquid contains at least one of a basic compound and an alkali generator, the rinse liquid may contain only one of the basic compound and the alkali generator, or may contain two or more of the basic compound and the alkali generator. When there are two or more of the basic compound and the alkali generator, the total amount of the basic compound and the alkali generator is preferably within the above range.

[0303] The rinsing solution may further comprise other ingredients.

[0304] Examples of other components include known surfactants and known defoaming agents.

[0305] [How to supply flushing fluid]

[0306] As long as the desired pattern can be formed, there is no particular restriction on the method of supplying the rinsing liquid. The following methods are available: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through liquid accumulation, a method of supplying the rinsing liquid to the substrate through spraying, and a method of continuously supplying the rinsing liquid to the substrate through means such as a straight nozzle.

[0307] From the perspectives of the permeability of the rinse liquid, the removal of the non-image area, and manufacturing efficiency, there are methods for supplying the rinse liquid using shower nozzles, straight nozzles, spray nozzles, etc. Continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, supply using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

[0308] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[0309] As a method for supplying the rinsing liquid in the rinsing step, a process of continuously supplying the rinsing liquid to the substrate, a process of maintaining the rinsing liquid in a substantially stationary state on the substrate, a process of vibrating the rinsing liquid on the substrate using ultrasonic waves, etc., and a combination of these processes can be adopted.

[0310] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10°C to 45°C, more preferably 18°C to 30°C.

[0311] In the development process, after processing with a developer or cleaning the pattern with a rinse solution, a process of bringing the treatment liquid into contact with the pattern may be included. Alternatively, a method of supplying the treatment liquid before the developer or rinse solution in contact with the pattern has completely dried may be adopted.

[0312] Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent and at least one of a basic compound and an alkali generator.

[0313] Preferred embodiments of the organic solvent, and at least one of the basic compound and the base generator are the same as preferred embodiments of the organic solvent, and at least one of the basic compound and the base generator used in the rinse solution.

[0314] The method of supplying the processing liquid to the pattern can be the same method as the method of supplying the rinse liquid described above, and the preferred aspects are also the same.

[0315] The content of the basic compound or base generating agent in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[0316] Furthermore, when the basic compound or base generator is solid in the environment where the treatment liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass relative to the total solid content of the treatment liquid.

[0317] When the treatment liquid contains at least one of an alkaline compound and an alkali generator, the treatment liquid may contain only one of the at least one of the alkaline compound and the alkali generator, or may contain two or more of the at least one of the alkaline compound and the alkali generator. When there are two or more of the at least one of the alkaline compound and the alkali generator, the total amount of the at least one of the alkaline compound and the alkali generator is preferably within the above range.

[0318] <Heating process>

[0319] The pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) can be subjected to a heating step of heating the pattern obtained by the development.

[0320] That is, the method for producing the first member of the present invention may include a heating step of heating the pattern obtained in the development step.

[0321] Furthermore, the heating step may be performed after the later-described conductive layer forming step, after the later-described polishing step, etc., as long as it is performed after the developing step, and the timing of the heating step is not particularly limited.

[0322] Furthermore, the method for manufacturing the first member of the present invention may include a heating step of heating a pattern obtained by another method without performing the development step or a film obtained by the film formation step.

[0323] In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide.

[0324] Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or a crosslinking agent other than the specific resin is also performed.

[0325] The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, further preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0326] The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by heating and utilizing the action of a base generated by the base generator.

[0327] Heating in the heating step is preferably performed at a heating rate of 1 to 12°C / minute from the heating start temperature to the maximum heating temperature. The heating rate is more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. A heating rate of 1°C / minute or higher ensures productivity and prevents excessive volatilization of the acid or solvent. A heating rate of 12°C / minute or lower mitigates residual stress in the cured product.

[0328] In the case of an oven capable of rapid heating, the temperature is preferably increased from the heating start temperature to the maximum heating temperature at a rate of 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0329] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the heating process to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, it refers to the temperature of the dried film (layer). For example, the temperature is preferably increased from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0330] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0331] Heating can be performed at a heating temperature of more than two stages. As an example, the following process can be performed: heating from 25°C to 150°C at a rate of 5°C / minute, maintaining at 150°C for 60 minutes, heating from 150°C to 230°C at a rate of 5°C / minute, and maintaining at 230°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is preferred to perform heat treatment while irradiating with ultraviolet rays. The properties of the film can be improved by this pretreatment process. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be set as a process of more than two stages. For example, the first stage pretreatment process can be performed in the range of 100 to 150°C, and then the second stage pretreatment process can be performed in the range of 150 to 230°C.

[0332] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[0333] The heating step is preferably performed under a low oxygen concentration environment, such as by flowing an inert gas such as nitrogen, helium, or argon under reduced pressure, from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[0334] The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0335] <Post-development exposure step>

[0336] The pattern obtained by the development step (the pattern after the rinsing step when the rinsing step is performed) may be subjected to a post-development exposure step for exposing the pattern after the development step instead of or in addition to the heating step.

[0337] That is, the method for manufacturing the first component of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step. The method for manufacturing the first component of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step.

[0338] In the post-development exposure step, for example, a cyclization reaction of a polyimide precursor or the like by sensitization to a photobase generator and a reaction of elimination of an acid-decomposable group by sensitization to a photoacid generator can be promoted.

[0339] In the post-development exposure step, at least a portion of the pattern obtained in the development step may be exposed, but it is preferred that the entire pattern be exposed.

[0340] The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm2 in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. 2 , more preferably 100 to 15,000 mJ / cm 2 .

[0341] The post-development exposure step can be performed, for example, using the light source used in the above-mentioned exposure step, and preferably using broadband light.

[0342] <Conductive Layer Formation Step>

[0343] The first component forming method of the present invention includes a conductive layer forming step of forming a conductive layer in a region between insulating patterns and on the insulating patterns of a substrate having insulating patterns formed thereon to obtain component A.

[0344] In the conductive layer forming step, the conductive layer can be formed by electroplating, applying a conductive paste, or the like.

[0345] The maximum thickness of the conductive layer formed in the conductive layer forming step is not particularly limited, but is preferably 500 to 10,000 nm, and more preferably 1,000 to 5,000 nm.

[0346] The conductive layer forming step can be performed, for example, by electrolytic copper plating. Here, in order to fill the area between the insulating patterns, it is preferred to use filled plating. Alternatively, it can be performed by electroless copper plating. These methods can be performed by known methods.

[0347] The conductive layer formed in the conductive layer forming step exists in the region between the insulating patterns and on the insulating patterns, and preferably fills the region between the insulating patterns and covers the insulating patterns.

[0348] Furthermore, the entire area between the insulating patterns does not necessarily need to be filled with the conductive layer. For example, the conductive layer can be formed along the inner walls (side surfaces and bottom surfaces) of these areas. In this manner, the areas not filled with the conductive layer can be removed by polishing in the polishing process described later, or the surface of the component can be flattened by polishing after forming the barrier layer described later.

[0349] <Seed Layer Formation Step>

[0350] The first component manufacturing method of the present invention preferably further includes a seed layer forming step of forming a seed layer (a feed layer for electrolytic copper plating) in a region between the insulating patterns before the conductive layer forming step.

[0351] The seed layer forming step is preferably a step of forming the seed layer along the inner walls (side surfaces and bottom surfaces) of the region between the insulating patterns.

[0352] Furthermore, in the seed layer forming step, the seed layer may also be formed above the insulating pattern. In this embodiment, the seed layer can be removed by polishing in the polishing step described later, thereby finally exposing the insulating pattern.

[0353] The seed layer is formed by, for example, sputtering.

[0354] Specifically, a seed layer can be formed by using a metal such as titanium or chromium as a sputtering target and introducing oxygen, nitrogen, etc. as a reaction gas. This can be done by a known method. Alternatively, a known method for forming a seed layer can be used.

[0355] The thickness of the seed layer is preferably 20 to 400 nm, more preferably 30 to 300 nm, and even more preferably 40 to 250 nm.

[0356] Furthermore, two or more seed crystal layers may be formed. When two or more seed crystal layers are formed, the thickness of each layer is preferably within the above range.

[0357] For example, after forming a seed layer based on titanium, chromium, nickel, or the like as the first layer, a seed layer based on a metal for a conductive layer such as copper may be formed as the second layer by electroplating or the like.

[0358] <Grinding process>

[0359] The first component manufacturing method of the present invention includes a polishing step of polishing component A to obtain a component in which the conductive pattern and the insulating pattern are exposed on the surface.

[0360] The grinding process is a process of grinding the member A to obtain a member with the conductive pattern and the insulating pattern exposed.

[0361] The surface of the conductive layer is removed by the polishing process to form a conductive pattern. In addition, when a seed layer is formed on the insulating pattern by the above method, it is preferable to remove the seed layer on the insulating pattern.

[0362] The polishing can be performed by physical polishing such as dicing, mechanical polishing, grinding, plasma treatment, and laser ablation, and is preferably performed by chemical polishing such as CMP (Chemical Mechanical Polishing), and more preferably performed by CMP.

[0363] The slurry used for the CMP is not particularly limited, and silicon dioxide slurry, ceria slurry, aluminum oxide slurry, titanium dioxide slurry, zirconium dioxide slurry, germanium oxide slurry, manganese oxide slurry, diamond slurry, etc. can be used. The size of the particles of the slurry is not particularly limited. From the viewpoint of suppressing scratch damage, it is preferably an average particle size of less than 1000nm, more preferably an average particle size of less than 500nm, and further preferably an average particle size of less than 200nm. The lower limit of the particle size of the slurry is not particularly limited. From the viewpoint of polishing rate, it is preferably more than 10nm.

[0364] Furthermore, CMP or the like may be performed after dicing, and these methods may be combined.

[0365] Examples of commercially available silica slurries include NP6220, NP6502, NP6504, NP6610, NP6605, NP8020H, NP8020, NP8030, NP8040, NP8040W, and EG1103 (all manufactured by NITTA DuPont Incorporated).

[0366] The content of particles such as silica, ceria, and alumina in the slurry is not particularly limited, but is preferably 0.01 to 80% by mass, more preferably 0.1 to 70% by mass, and even more preferably 0.2 to 60% by mass relative to the total mass of the slurry from the viewpoint of suppressing scratches.

[0367] In this specification, the content of each component in the slurry is described as the content of each component when the slurry is used for polishing. When the slurry is diluted with water or a solvent during polishing, it refers to the content in the diluted composition.

[0368] Furthermore, as the particles, two kinds of particles made of different materials or two kinds of particles having different particle sizes may be used in combination. In these cases, the total content of the particles preferably satisfies the above numerical range.

[0369] 〔Oxidant〕

[0370] Furthermore, the slurry preferably contains an oxidizing agent. It is believed that the oxidizing agent acts on the surface of the insulating pattern, making the insulating pattern easier to remove, thereby increasing the etching rate.

[0371] Examples of the oxidizing agent include hydrogen peroxide, peroxides, nitrates, iodates, periodates, hypochlorites, chlorites, chlorates, perchlorates, persulfates, dichromates, permanganates, ozone water, silver (II) salts, and iron (III) salts.

[0372] The amount of the oxidizing agent used is preferably 0.0001 to 20 mol, more preferably 0.001 to 15 mol, and even more preferably 0.001 to 10 mol per 1 L of the slurry.

[0373] Furthermore, two or more oxidizing agents may be used simultaneously. In this case, the total content of the oxidizing agents preferably satisfies the above numerical range.

[0374] pH adjuster

[0375] The slurry preferably contains a pH adjuster.

[0376] By including a pH adjuster, the pH during polishing can be kept constant, and effects such as suppressing variations in polishing can be achieved.

[0377] Examples of the pH adjuster include acidic compounds, basic compounds, and pH buffers, and a basic compound is preferably included.

[0378] As the acidic compound, an inorganic acid can be used. Examples of inorganic acids include, but are not limited to, sulfuric acid, nitric acid, boric acid, and phosphoric acid. Among these inorganic acids, sulfuric acid, nitric acid, and phosphoric acid are preferably used.

[0379] Examples of the alkaline compound include ammonium hydroxide, organic ammonium hydroxides such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TMAH), ethylenediamine, butylene diamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, refined triamine, diaminocyclohexane, and amine compounds such as bis(2-methoxyethyl)amine. , alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, carbonates, phosphates, borates, tetraborates, hydroxybenzoates, aminoacetyl salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxymethylaminomethane salts, lysine salts, etc., but are not limited to these.

[0380] Examples of pH buffers include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), ammonium hydroxide, and the like. Examples of pH buffers include amino acids or amino acid derivatives such as glycine, alanine, and N-methylglycine, and organic acids such as butyric acid and glycolic acid. However, usable pH buffers are not limited to these.

[0381] The amount of the pH adjuster added is not particularly limited as long as it is an amount that can adjust the pH of the slurry to a target value, and the compound or amount to be added may be appropriately adjusted depending on the purpose.

[0382] The pH can be arbitrarily selected. For example, from the viewpoint of polishing rate, it is sometimes preferable to adjust to the alkaline side of pH 8 to 14.

[0383] Furthermore, the slurry can be prepared at a low pH, and the optimal pH can be appropriately selected in consideration of the polishing rate, the corrosion resistance of adjacent metals, and the like.

[0384] 〔preservative〕

[0385] The above slurry preferably contains a corrosion inhibitor.

[0386] By including the corrosion inhibitor, for example, corrosion of metal (eg, copper) in the conductive pattern can be suppressed.

[0387] Examples of the corrosion inhibitor include heteroaromatic compounds.

[0388] Furthermore, as the corrosion inhibitor, a compound that forms a passivation film on the metal surface to be polished is preferable.

[0389] The "heteroaromatic ring compound" refers to a compound having a ring structure containing a heteroatom as one or more ring-constituting atoms.

[0390] The heteroatom is preferably a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom or a boron atom, more preferably a nitrogen atom, a sulfur atom, an oxygen atom or a selenium atom, particularly preferably a nitrogen atom, a sulfur atom or an oxygen atom, and most preferably a nitrogen atom or a sulfur atom.

[0391] The heteroaromatic ring compound is not particularly limited, and examples thereof include compounds described in paragraphs 0027 to 0035 of JP-A-2009-224695.

[0392] The content of the corrosion inhibitor is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.0005 to 0.05 mol per 1 L of the slurry.

[0393] Furthermore, two or more corrosion inhibitors may be used simultaneously. In this case, the total content of the corrosion inhibitors preferably satisfies the above-mentioned numerical range.

[0394] 〔Other additives〕

[0395] The slurry may contain various known additives depending on the purpose.

[0396] Examples of known additives include surfactants, solvents, and chelating agents, but are not limited thereto.

[0397] -Surfactants-

[0398] The slurry preferably contains a surfactant.

[0399] Inclusion of a surfactant may sometimes provide an effect of protecting the metal film and suppressing excessive polishing.

[0400] Examples of the surfactant include anionic, cationic, nonionic, and amphoteric (betaine) surfactants.

[0401] These surfactants are not particularly limited, and examples thereof include compounds described in paragraphs 0038 to 0047 of JP-A-2009-224695.

[0402] The amount of the surfactant added is preferably 0.0001 to 10 g, more preferably 0.0005 to 5 g, and particularly preferably 0.0005 to 3 g per 1 L of the slurry.

[0403] Furthermore, two or more surfactants may be used simultaneously. In this case, the total content of the surfactants preferably satisfies the above numerical range.

[0404] -Solvents-

[0405] The slurry may contain a solvent.

[0406] Examples of the solvent include water and organic solvents.

[0407] Examples of organic solvents include polar solvents such as alcohols and acetic acid. Furthermore, to improve wettability with the polished surface and to achieve similar polishing rates for the interlayer insulating film and barrier film, examples include ethylene glycols, ethylene glycol monoethers, ethylene glycol diethers, alcohols, carbonates, lactones, ethers, ketones, phenols, dimethylformamide, N-methylpyrrolidone, ethyl acetate, ethyl lactate, sulfolane, and sulfoxides. Among these, at least one selected from dimethyl sulfoxide, ethylene glycol monoethers, alcohols, and carbonates is preferred.

[0408] The solvent may be supplied during polishing or added to the slurry before polishing. The amount of solvent used may be appropriately set in consideration of the state of the surface being polished.

[0409] When an organic solvent is added, the content of the organic solvent is preferably 0.01 to 90 parts by mass relative to 100 parts by mass of the slurry used during polishing. From the perspective of improving the wettability of the slurry to the substrate during polishing, the above content is more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more. Furthermore, from the perspective of facilitating the manufacturing process, the upper limit is more preferably 50 parts by mass or less, and even more preferably 10 parts by mass or less.

[0410] Polishing is performed to remove the portion of the conductive layer formed on the insulating pattern and, if present, the seed layer, until the conductive layer and insulating pattern are exposed. However, polishing can also be performed to polish the upper surface of the insulating pattern. This method can sometimes improve the flatness of the component surface.

[0411] Here, for example, when the above-mentioned seed layer is present, two-stage polishing may be performed.

[0412] Specifically, there is a method in which the conductive layer is removed by first-stage polishing to the surface of the seed layer to expose the seed layer, and then the seed layer is removed by second-stage polishing to expose the insulating pattern.

[0413] The difference between the maximum and minimum values of the distance from the polished substrate to the surface of the conductive pattern on the opposite side to the substrate is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.

[0414] <Barrier Layer Formation Step>

[0415] The method for manufacturing the first member of the present invention preferably further includes a barrier layer forming step of forming a barrier layer on the conductive pattern after the polishing step.

[0416] The barrier layer is formed on the exposed surface of the conductive pattern exposed by the polishing process.

[0417] By forming the barrier layer, diffusion of the metal constituting the conductive pattern is suppressed.

[0418] The material constituting the barrier layer is not particularly limited, and known materials can be used, including SiN 2 , TiN, cobalt compounds, nickel, and the like.

[0419] The barrier layer is not particularly limited as to the method for forming it, and a known method can be used. However, the barrier layer can also be formed by electroless plating or the like.

[0420] The thickness of the barrier layer is not particularly limited, but is preferably 50 to 500 nm, more preferably 100 to 400 nm, and even more preferably 150 to 300 nm.

[0421] <Other Processes>

[0422] The method for manufacturing the first member of the present invention may further include other steps known in the art.

[0423] <Example of the Manufacturing Method of the First Component>

[0424] Hereinafter, an example of a method for manufacturing the first component of the present invention will be described using the drawings. In the drawings, already described and duplicated symbols may be omitted. Furthermore, the dimensional ratios of the components in the drawings may not be accurate.

[0425] Figure 4 It is a process explanatory diagram schematically showing the steps of the method for manufacturing the first component according to one embodiment of the present invention using cross-sectional views.

[0426] exist Figure 4 (a) shows a state where insulating patterns 102 are formed on a substrate 100. The insulating patterns 102 have regions 103 between the insulating patterns.

[0427] Figure 4 (b) is Figure 4 (a) shows a state where a seed layer 104 and a conductive layer 105 are formed on the region 103 between the insulating patterns and the insulating pattern 102 . Figure 4 (b) shows the part corresponding to the above-mentioned part A.

[0428] Figure 4 (c) grinding Figure 4 (b) shows a state where the component A has the insulating pattern 102 and the conductive pattern 106 formed thereon.

[0429] And, for Figure 4 In the component shown in (c), a barrier layer may be further formed on the conductive pattern 106 .

[0430] <Method for Manufacturing the Second Component>

[0431] The manufacturing method of the component of the second embodiment of the present invention (also referred to as "the manufacturing method of the second component") comprises a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on the surface of at least a portion of the first insulating pattern, and a conductive pattern that conducts the area between the first insulating pattern and the area between the second insulating pattern. The manufacturing method of the component comprises steps A to C, and the angle formed by the bottom surface of the conductive pattern of the component and the side surface of the conductive pattern exceeds 90° and is less than 110°.

[0432] Step A: Preparing a component A including the first insulating pattern and the second insulating pattern

[0433] Step B: forming a conductive layer on the area between the first insulating patterns, the area between the second insulating patterns, and the second insulating patterns of the component A to obtain a conductive layer forming step of component B

[0434] Step C: Polishing the component B to obtain a component where the conductive pattern and the second insulating pattern are exposed.

[0435] According to the second member manufacturing method of the present invention, the above-mentioned second member of the present invention is manufactured.

[0436] That is, the angle (first pattern angle) between the substrate, the first insulating pattern, the second insulating pattern, the conductive pattern, and the angle between the bottom surface of the above-mentioned conductive pattern and the side surface of the conductive pattern in the manufactured component are as described above, and the preferred embodiments of these are also the same as those in the above-mentioned second component.

[0437] <Process A>

[0438] The method for manufacturing the second component of the present invention includes a preparation step (step A) of preparing a component A including the first insulating pattern and the second insulating pattern.

[0439] In the preparation step, the component A may be manufactured by a known method or may be obtained by purchasing or the like.

[0440] Next, a manufacturing method for manufacturing component A will be described.

[0441] The manufacturing method of component A preferably includes a first film forming step of applying a photosensitive resin composition (a first insulating pattern forming composition) to a substrate to form a film, a first exposure step of selectively exposing the film formed by the first film forming step, a first developing step of developing the film exposed by the first exposure step using a developer to form a first insulating pattern, a second film forming step of applying a photosensitive resin composition (a second insulating pattern forming composition) to the above-mentioned first insulating pattern to form a film, a second exposure step of selectively exposing the film formed by the second film forming step, and a second developing step of developing the film exposed by the second exposure step using a developer to form a second insulating pattern.

[0442] Furthermore, in the manufacturing method of component A, the first insulating pattern may be formed by etching or the like instead of the first exposure step and the first development step, and the second insulating pattern may be formed by etching or the like instead of the second exposure step and the second development step.

[0443] Hereinafter, the details of each step will be described.

[0444] The details of each photosensitive resin composition (hereinafter, also simply referred to as a “resin composition”) will be described later.

[0445] [First film forming step]

[0446] The method for producing a cured product of the present invention preferably includes a first film-forming step of applying the photosensitive resin composition on a substrate to form a film.

[0447] The substrate in the first film-forming step is as described above.

[0448] As a method of applying the resin composition, the same method as that in the film forming step in the method for producing the first member of the present invention can be used, and preferred aspects are also the same.

[0449] [First exposure step]

[0450] The film formed in the first film forming step may be subjected to a first exposure step of selectively exposing the film to light.

[0451] The first exposure step can be performed by the same method as the exposure step in the above-mentioned method for producing the first member of the present invention, and the preferred embodiment is also the same.

[0452] [First post-exposure heating step]

[0453] The film may be subjected to a step of heating after exposure (first post-exposure heating step).

[0454] The first post-exposure heating step can be performed by the same method as the post-exposure heating step in the above-mentioned method for producing the first member of the present invention, and the preferred embodiment is also the same.

[0455] [First Development Step]

[0456] The film after exposure can be subjected to a first development step of developing with a developer to form a pattern.

[0457] The first development step can be performed by the same method as the development step in the above-mentioned method for producing the first member of the present invention, and the preferred embodiment is also the same.

[0458] [First heating step]

[0459] The developed film may be subjected to a first heating step of heating the film.

[0460] The first heating step can be performed by the same method as the heating step in the above-mentioned method for producing the first member of the present invention, and the preferred embodiment is also the same.

[0461] Furthermore, heating may not be performed at this point, but the first insulating pattern and the second insulating pattern may be heated together after the second insulating pattern described later is formed.

[0462] This heating may be performed after the conductive layer forming step, before the polishing step, or after the polishing step.

[0463] [First post-processing step]

[0464] After the first development step, a first post-processing step of performing post-processing by at least one of heating and exposure may be performed.

[0465] The heating temperature is preferably 100 to 160°C, more preferably 120 to 160°C.

[0466] Examples of the exposure include exposure at 1,000 to 50,000 mJ / cm2 by the same method as in the above-mentioned exposure step. 2 Methods of exposing the entire surface with a certain exposure amount, etc.

[0467] [Second film forming step]

[0468] The method for producing the component A preferably includes a second film forming step of applying a photosensitive resin composition to the first insulating pattern to form a film.

[0469] The second film forming step can be performed by the same method as the first film forming step described above, except that the photosensitive resin composition is applied to the first insulating pattern instead of the substrate, and the preferred embodiment is also the same.

[0470] [Second exposure step, second development step]

[0471] The second exposure step and the second development step can be performed by the same method as the first exposure step and the first development step, and preferred aspects are also the same.

[0472] Furthermore, a second post-exposure heating step performed similarly to the above-mentioned first post-exposure heating step may be included after the second exposure step.

[0473] Furthermore, a second post-processing step performed similarly to the above-mentioned first post-processing step may be included after the second development step.

[0474] [Second heating step]

[0475] The developed film may be subjected to a second heating step of heating the film.

[0476] The second heating step can be performed by the same method as the heating step in the method for producing the first member of the present invention described above, and the preferred embodiment is also the same.

[0477] Furthermore, heating may not be performed at this point, but the first insulating pattern and the second insulating pattern may be heated together after the second insulating pattern described later is formed.

[0478] This heating may be performed after the conductive layer forming step, before the polishing step, or after the polishing step.

[0479] <Process B>

[0480] In the manufacturing method of the second component of the present invention, as step B, a conductive layer forming step is included for forming a conductive layer on the area between the first insulating patterns, the area between the second insulating patterns, and the second insulating patterns of the above-mentioned component A to obtain component B.

[0481] Step B can be performed by the same method as the conductive layer forming method in the above-mentioned method for producing the first member of the present invention, and the preferred embodiment is also the same.

[0482] <Seed Layer Formation Step>

[0483] The method for manufacturing the second member of the present invention preferably further includes, between step A and step B, a seed layer forming step of forming a seed layer in the region between the first patterns and the region between the second patterns.

[0484] The seed layer forming step is preferably a step of forming the seed layer along the inner walls (side surfaces and bottom surfaces) of the region between the first patterns and the region between the second patterns.

[0485] Furthermore, in the seed layer forming step, a seed layer may also be formed on the second pattern. In this embodiment, the seed layer can be removed by polishing in step C described later to finally expose the second insulating pattern.

[0486] The seed layer forming step can be performed by the same method as the seed layer forming step in the above-mentioned method for manufacturing the first member of the present invention, and the preferred embodiment is also the same.

[0487] <Process C>

[0488] The method for manufacturing the second member of the present invention includes, as step C, a polishing step of polishing the member B to obtain a member in which the conductive pattern and the second insulating pattern are exposed.

[0489] The surface of the conductive layer is removed by the polishing step to form a conductive pattern. In addition, when a seed layer is formed by the above method, it is preferable to also remove the seed layer.

[0490] The polishing step can be performed by the same method as the polishing step in the method for producing the first member of the present invention described above, and the preferred embodiment is also the same.

[0491] <Barrier Layer Formation Step>

[0492] The method for manufacturing the second member of the present invention preferably further includes, after step C, a barrier layer forming step of forming a barrier layer on the conductive pattern.

[0493] The barrier layer is formed on the exposed surface of the conductive pattern exposed in step C.

[0494] By forming the barrier layer, diffusion of the metal constituting the conductive pattern is suppressed.

[0495] The barrier layer forming step can be performed by the same method as the polishing step in the above-mentioned method for producing the first member of the present invention, and the preferred embodiment is also the same.

[0496] <Barrier Layer Polishing Step>

[0497] The method for manufacturing the second member of the present invention may further include a barrier layer forming step of polishing the barrier layer.

[0498] The barrier layer polishing step is not particularly limited and can be performed by a known method, for example, the same method as the above-mentioned step C.

[0499] <Other Processes>

[0500] The method for manufacturing the second member of the present invention may further include other steps known in the art.

[0501] <Example of the Manufacturing Method of the Second Component>

[0502] The following is an example of a method for manufacturing the second component of the present invention, using the drawings. In the drawings, overlapping symbols that have already been described may be omitted. Furthermore, the dimensional ratios of the components in the drawings may not be accurate.

[0503] Figure 5 This is a process explanatory diagram schematically showing (part of) the process of the method for manufacturing the second component according to one embodiment of the present invention using a cross-sectional view.

[0504] exist Figure 5 (a) shows a substrate 1 having an insulating pattern 4 and a conductive pattern 6 formed on a silicon wafer 2. Such a substrate can be manufactured by a conventional method or can be purchased.

[0505] Figure 5 (b) shows a state where the photosensitive resin composition for forming the first insulating pattern is applied to the substrate 1 and a film 10 is formed.

[0506] Figure 5 (c) indicates Figure 5 The film 10 in (b) is exposed and developed to form a hole pattern 12 as the first insulating pattern 14 before curing.

[0507] Figure 5 (d) shows a state where the second photosensitive resin composition is applied to the film 10 having the hole pattern 12 formed thereon to form the film 20 .

[0508] Figure 5 (e) represents the following state: a line and space pattern (space portion) 22 is formed on the membrane 20 in such a manner that the space portion is located on the hole pattern of the membrane 10 and serves as the second insulating pattern before curing. On this basis, the first insulating pattern before curing is changed to the first insulating pattern 16 by heating, and the second insulating pattern before curing is changed to the second insulating pattern 26.

[0509] Here, Figure 5 The component shown in (e) corresponds to an example of component A in step A.

[0510] Figure 6 This is a process explanation diagram schematically showing (part of) the process of the method for manufacturing the second component according to one embodiment of the present invention in cross-sectional view (continued) Figure 5 ).

[0511] Figure 6 (a) shows a state where the seed layer 42 is formed so as to cover the first insulating pattern 16 and the second insulating pattern 26 (seed layer forming step).

[0512] Figure 6(b) shows a state where the conductive layer 44 is formed on the seed layer 42 by copper plating (step B).

[0513] Figure 6 (c) shows a state where the conductive layer 44 and the seed layer 42 are removed by the polishing process, and the conductive pattern 46 and the second insulating pattern 26 are exposed (process C).

[0514] Figure 6 The member shown in (c) corresponds to an example of the second member of the present invention.

[0515] And, for Figure 6 The second member shown in (c) may further include a barrier layer formed on the conductive pattern 46 .

[0516] (Photosensitive resin composition)

[0517] The following describes in detail the photosensitive resin composition used to form the insulating pattern in the method for manufacturing the first component of the present invention (insulating pattern-forming composition), the photosensitive resin composition used to form the first insulating pattern in the method for manufacturing the first component (first insulating pattern-forming composition), and the photosensitive resin composition used to form the second insulating pattern (second insulating pattern-forming composition). These three compositions are also collectively referred to as the "photosensitive resin composition."

[0518] The first insulating pattern forming composition and the second insulating pattern forming composition may have the same composition or different compositions.

[0519] Furthermore, the photosensitive resin composition of the present invention is a photosensitive resin composition for forming an insulating pattern used in the method for producing the first member of the present invention.

[0520] Hereinafter, the details of each component contained in the photosensitive resin composition of the present invention will be described.

[0521] <Specific resin>

[0522] The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.

[0523] The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.

[0524] In the present invention, the "main chain" refers to the relatively longest bond chain in the resin molecule, and the "side chain" refers to the other bond chains.

[0525] Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamide amide.

[0526] The precursor of the cyclized resin is a resin whose chemical structure changes under external stimulation to become a cyclized resin, preferably a resin whose chemical structure changes under heat to become a cyclized resin, and more preferably a resin which forms a ring structure by a ring-closing reaction caused by heat.

[0527] Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.

[0528] That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamideimide, and a polyamideimide precursor.

[0529] The resin composition preferably contains a polyimide or a polyimide precursor as the specific resin.

[0530] The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0531] When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably a radical polymerization initiator and a radical crosslinking agent. A sensitizer may also be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition.

[0532] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0533] When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. For example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed from such a resin composition.

[0534] 〔Polyimide precursor〕

[0535] The polyimide precursor used in the present invention is not particularly limited in its type and the like, but preferably contains a repeating unit represented by the following formula (2).

[0536] [Chemical Formula 1]

[0537]

[0538] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0539] A in formula (2) 1 and A 2 Each independently preferably represents an oxygen atom or -NR z -, oxygen atom.

[0540] R z represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0541] R in formula (2) 111 Represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, preferably an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group in the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, preferably -Ar-L-Ar-. Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of a combination of two or more of the foregoing. The preferred ranges are as described above.

[0542] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic, or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0543] Specifically, R 111 Preferred are diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably diamines containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon groups in the linear or branched aliphatic groups may be substituted with groups containing heteroatoms, and the hydrocarbon groups in the ring members of the cyclic aliphatic and aromatic groups may be substituted with groups containing heteroatoms. Examples of groups containing aromatic groups include the following.

[0544] [Chemical Formula 2]

[0545]

[0546] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0547] Where * indicates the bonding position with other structures.

[0548] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane.

[0549] 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine;

[0550] m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2, 2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4' -dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, At least one diamine selected from 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

[0551] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0552] Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0553] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group herein is preferably an alkylene group.

[0554] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred.

[0555] Formula (51)

[0556] [Chemical Formula 3]

[0557]

[0558] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to the nitrogen atom in formula (2).

[0559] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0560] [Chemical Formula 4]

[0561]

[0562] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to the nitrogen atom in formula (2).

[0563] Examples of the diamine that imparts the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

[0564] Furthermore, R is also preferred. 111 is a group represented by the following formula (71). In the above embodiment, it is more preferable that R 111 It is a group represented by the following formula (72).

[0565] [Chemical Formula 5]

[0566]

[0567] In formula (71), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, * represents the bonding position to the nitrogen atom in formula (2), and the four benzene rings described in formula (71) may each have a substituent.

[0568] In formula (72), * represents the bonding position to the nitrogen atom in formula (2).

[0569] In formula (71), A1 ~A 3 Preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group consisting of a combination of two or more of these. More preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, or a group consisting of a combination of two or more of these. Still more preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms or -O-.

[0570] In particular, A is preferred 1 and A 3 It is -O-.

[0571] In particular, A is preferred 2 It is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.

[0572] Among these, A 1 and A 3 For -O- and A 2 The embodiment of -C(CH3)2- is also one of the preferred embodiments of the present invention.

[0573] The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4.

[0574] Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH2-, -C(CH3)2-, and -C(CF3)2-, among which -C(CH3)2- is preferred.

[0575] Examples of the substituents on the four benzene rings described in formula (71) include fluorine atoms and hydrocarbon groups having 1 to 10 carbon atoms in which hydrogen atoms may be substituted by fluorine atoms.

[0576] Furthermore, an embodiment in which all four benzene rings described in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

[0577] Furthermore, R is also preferred. 111 is a group represented by the following formula (81). In the above embodiment, it is more preferable that R 111 It is a group represented by the following formula (82).

[0578] [Chemical Formula 6]

[0579]

[0580] In formula (81), A 1 and A 2Each independently represents a single bond or a divalent linking group, * represents the bonding position to the nitrogen atom in formula (2), and the three benzene rings described in formula (81) may each have a substituent.

[0581] In formula (82), * represents the bonding position to the nitrogen atom in formula (2).

[0582] In formula (81), A 1 and A 2 Preferably, each independently, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group consisting of a combination of two or more of these. More preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, or a group consisting of a combination of two or more of these. Further preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom or -O-, and particularly preferably -C(CH3)2-.

[0583] R in formula (2) 115 The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[0584] In formula (5) or formula (6), * each independently represents a bonding position to another structure.

[0585] [Chemical Formula 7]

[0586]

[0587] In formula (5), R 112 It is a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, further preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0588] Furthermore, R is also preferred. 115 is a group represented by the following formula (7). In the above embodiment, it is preferred that R 115 It is a group represented by the following formula (7-2).

[0589] [Chemical Formula 8]

[0590]

[0591] In formula (7), A 1 ~A 3 Each of them is independently a single bond or a divalent linking group, * represents the bonding position to the carbonyl group in formula (2), and the four benzene rings described in formula (7) may each have a substituent.

[0592] In this specification, a bond that crosses the side of a ring structure means a bond that replaces any of the hydrogen atoms in the ring structure.

[0593] In formula (7-2), * represents a bonding position to the carbonyl group in formula (2).

[0594] In formula (7), A 1 ~A 3 , and the preferred embodiment of the substituents in the benzene ring is the same as that of A in the above formula (71). 1 ~A 3 , and the preferred embodiments of the substituents in the benzene ring are the same.

[0595] Furthermore, R is also preferred. 115 is a group represented by the following formula (8). In the above embodiment, R 115 It is a group represented by the following formula (8-2).

[0596] [Chemical Formula 9]

[0597]

[0598] In formula (8), A 4 and A 5 are independently -C(=O)-O- or -C(=O)NH-, L 1 is a divalent linking group, * represents the bonding position to the carbonyl group in formula (2), and the two benzene rings described in formula (8) may each have a substituent.

[0599] A 4 and A 5 An embodiment in which one of them is -C(=O)-O- and the other is -C(=O)NH- is also one of the preferred embodiments of the present invention.

[0600] Here, the orientation of the -C(=O)-O- is not particularly limited. It is preferred that the carbon atom in -C(=O)-O- is bonded to L by a single bond without a linking group. 1 bond.

[0601] Furthermore, the orientation of the -C(=O)-NH- is not particularly limited. It is preferred that the carbon atom in -C(=O)-NH- is bonded to L by a single bond without a linking group. 1 bond.

[0602] L 1 It is preferably a hydrocarbon group which may have a substituent, more preferably an aromatic hydrocarbon group, and still more preferably a phenylene group.

[0603] L 1 The hydrocarbon group in the group may have a substituent. Examples of the substituent include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.

[0604] In formula (8-2), R each independently represents a substituent, n is an integer of 0 to 4, and * represents a bonding position to the carbonyl group in formula (2).

[0605] R is preferably each independently a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and preferably a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.

[0606] n is preferably an integer of 0 to 2. Furthermore, an embodiment in which n is 2 is also one of the preferred embodiments of the present invention.

[0607] Specifically, R 115 Examples include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. 115 The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues.

[0608] Tetracarboxylic dianhydride is preferably represented by the following formula (0).

[0609] [Chemical Formula 10]

[0610]

[0611] In formula (0), R 115 Represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The meanings are the same and the preferred ranges are also the same.

[0612] Specific examples of tetracarboxylic dianhydrides include pyromellitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

[0613] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned as preferred examples.

[0614] In formula (2), R 111 and R 115 At least one of R may also have an OH group. More specifically, 111 , for example, residues of bisaminophenol derivatives.

[0615] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferred to include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. In addition, it is preferred that R 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114At least one of the polyimide precursors contains more than two polymerizable groups. As a polymerizable group, it is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As the free radical polymerizable group possessed by the polyimide precursor, a group with an ethylenically unsaturated bond is preferably present.

[0616] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). Preferred groups include a group represented by the following formula (III).

[0617] [Chemical Formula 11]

[0618]

[0619] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and preferably a hydrogen atom or a methyl group.

[0620] In formula (III), * represents a bonding position with other structures.

[0621] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group.

[0622] Preferred R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. Alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups are more preferred. Alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are further preferred.

[0623] In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0624] When the polyalkyleneoxy group includes a plurality of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an alternating arrangement.

[0625] The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0626] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0627] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0628] From the perspective of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups are bonded to multiple propyleneoxy groups. A polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which multiple ethyleneoxy groups are bonded to multiple propyleneoxy groups, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0629] In formula (2), when R 113 When it is a hydrogen atom or R 114 When it is a hydrogen atom, the polyimide precursor can form a salt pair with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0630] In formula (2), R 113 and R 114 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. Preferred groups include acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups. From the perspective of exposure sensitivity, acetal groups and ketal groups are more preferred.

[0631] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl and tetrahydrofuranyl are preferred.

[0632] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0633] Furthermore, in order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0634] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), the exposure latitude can be further increased.

[0635] Formula (2-A)

[0636] [Chemical Formula 12]

[0637]

[0638] In formula (2-A), A 1 and A 2 represents oxygen atom, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, and preferably both of them are groups containing a polymerizable group.

[0639] A 1 、A 2 、R 111 、R 113 and R 114 The meanings of are independently the same as those of A in formula (2) 1 、A 2 、R 111 、R 113 and R 114 The meanings and preferred ranges are the same. 112 The meaning of is the same as R in formula (5) 112 The meanings and preferred ranges are the same.

[0640] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating units represented by formula (2). In addition to the repeating units represented by formula (2), the polyimide precursor may also contain other types of repeating units.

[0641] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) can be 50 mol% or more of the total repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminal can be repeating units represented by formula (2).

[0642] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0643] The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0644] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0645] When the resin composition contains multiple polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor be within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polyimide precursors, calculated as a single resin, be within the above ranges.

[0646] 〔Polyimide〕

[0647] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent.

[0648] In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the perspective of pattern formation, the polyimide preferably dissolves 0.5 g or more, and more preferably dissolves 1.0 g or more. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less.

[0649] From the viewpoint of film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0650] -Fluorine atom-

[0651] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has fluorine atoms.

[0652] For example, the fluorine atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described later 131 Among them, R is more preferably included as a fluorinated alkyl group in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by the formula (4) described later 131 middle.

[0653] The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and preferably 20% by mass or less.

[0654] -Silicon atoms-

[0655] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has a silicon atom.

[0656] For example, the silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 131 Among them, R is more preferably included in the repeating unit represented by the formula (4) described later as an organo-modified (poly)siloxane structure described later. 131 middle.

[0657] The silicon atom or the organo-modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.

[0658] The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0659] -Ethylenically unsaturated bond-

[0660] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0661] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0662] The ethylenically unsaturated bond is preferably radically polymerizable.

[0663] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 Among them, it is more preferable that the group having an ethylenically unsaturated bond is contained in R 132 or R 131 middle.

[0664] Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 131 Among them, it is more preferable that the group having an ethylenically unsaturated bond is contained in R 131 middle.

[0665] Examples of the group having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0666] [Chemical Formula 13]

[0667]

[0668] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0669] In formula (IV), R 21 It represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, and the number of repetitions of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a group formed by combining two or more of these.

[0670] The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or a combination thereof.

[0671] The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0672] Among these, R 21It is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).

[0673] [Chemical Formula 14]

[0674]

[0675] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding position to other structures, and ● represents the bonding position to R in formula (IV). 21 The bonding position of the bonded oxygen atom.

[0676] In formulas (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is the same as that of R in formula (IV). 21 The preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms is the same.

[0677] In formula (R1), X is preferably an oxygen atom.

[0678] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.

[0679] The structure represented by formula (R1) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).

[0680] The structure represented by formula (R2) can be obtained by, for example, reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0681] The structure represented by formula (R3) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0682] In formula (IV), * represents a bonding position to another structure, and is preferably a bonding position to the main chain of the polyimide.

[0683] The amount of the ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g, relative to the total mass of the polyimide.

[0684] -Polymerizable groups other than groups having an ethylenically unsaturated bond-

[0685] The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.

[0686] Examples of polymerizable groups other than the group having an ethylenically unsaturated bond include epoxy groups, cyclic ether groups such as oxetane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups.

[0687] For example, a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included in R in the repeating unit represented by the formula (4) described later. 131 .

[0688] The amount of the polymerizable groups other than the group having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0689] -Polarity conversion group-

[0690] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same, and preferred embodiments are also the same.

[0691] The polarity conversion group is included in, for example, R in the repeating unit represented by the formula (4) described below. 131 、R 132 , the end of polyimide, etc.

[0692] -Acid value-

[0693] When the polyimide is used for alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more, from the viewpoint of improving developability.

[0694] The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0695] When the polyimide is used for development using a developer containing an organic solvent as the main component (eg, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0696] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0697] As the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferably an acid group, and an acid group having a pKa of 3 to 8 is more preferably an acid group, from the viewpoint of achieving both storage stability and developability.

[0698] The pKa is a value representing the equilibrium constant, Ka, by its negative common logarithm, pKa, taking into account the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is a value calculated based on ACD / ChemSketch (registered trademark). For pKa, reference can be made to the values listed in "Chemical Handbook, 5th Edition, Revised Basics," edited by the Chemical Society of Japan.

[0699] When the acid group is a polyacid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant.

[0700] As such an acid group, the polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0701] -Phenolic hydroxyl group-

[0702] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0703] The polyimide may have a phenolic hydroxyl group at a main chain terminal or in a side chain.

[0704] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 .

[0705] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g, relative to the total mass of the polyimide.

[0706] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

[0707] [Chemical Formula 15]

[0708]

[0709] In formula (4), R 131 represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0710] In the case of having a polymerizable group, the polymerizable group may be located at R 131 and R 132At least one of them may be located at a terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0711] Formula (4-1)

[0712] [Chemical Formula 16]

[0713]

[0714] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as those in formula (4).

[0715] Formula (4-2)

[0716] [Chemical Formula 17]

[0717]

[0718] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as those in formula (4).

[0719] Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond and a crosslinkable group other than a group having the above-mentioned ethylenically unsaturated bond.

[0720] R 131 The divalent organic group includes the following: 111 The preferred ranges are also the same.

[0721] As R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 example.

[0722] From the perspective of more effectively suppressing warpage during calcination, R 131 A diamine residue having at least two alkylene glycol units in the main chain is preferred. A diamine residue containing two or more ethylene glycol chains or propylene glycol chains or both in one molecule is more preferred. A diamine residue containing no aromatic ring is further preferred.

[0723] Examples of diamines containing two or more ethylene glycol chains or propylene glycol chains or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by Huntsman Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0724] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include the following: 115 The preferred ranges are also the same.

[0725] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in formula (4) to form a condensed ring.

[0726] R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0727] It is also preferred that R 131 and R 132 More specifically, as R 131 As preferred examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) can be cited as R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be cited.

[0728] Furthermore, the polyimide preferably contains a repeating unit represented by the following formula (4-3) as the repeating unit represented by the formula (4).

[0729] [Chemical Formula 18]

[0730]

[0731] In formula (4-3), X1 represents an organic group with 4 or more carbon atoms, Y 1 represents an organic group with more than 4 carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0732] [Chemical Formula 19]

[0733]

[0734] In formula (R-1), L 1 Represents a2+1 valence connecting group, A 1 represents a polymerizable group, a2 represents an integer greater than 1, and * represents the same as X in formula (4-3). 1 or Y 1 bonding position.

[0735] -R 1 -

[0736] R 1 Each independently represents the structure represented by formula (R-1).

[0737] In formula (R-1), L 1 It represents a2+1 valence linking group.

[0738] L 1 Preferred is a group represented by the following formula (LR-1).

[0739] [Chemical Formula 20]

[0740]

[0741] In formula (LR-1), L x represents a2+1 valence linking group, a2 represents an integer greater than 1, and * represents the same as X in formula (4-3) 1 or Y 1 The bonding position of A in formula (R-1) is represented by #. 1 The bond position.

[0742] L x An alkylene group is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred.

[0743] Preferred aspects of a2 in formula (LR-1) are the same as preferred aspects of a2 in formula (R-1).

[0744] -A 1 -

[0745] A in formula (R-1) 1represents a polymerizable group, and preferred embodiments of the polymerizable group are the same as those of the polymerizable group in the above-mentioned specific resin.

[0746] Among them, A in formula (R-1) contained in formula (4-3) 1 At least one of them is preferably a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, and more preferably a vinylphenyl group.

[0747] -a2-

[0748] In formula (R-1), a2 represents an integer of 1 or greater, preferably 1 or 2, and more preferably 1.

[0749] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0750] -X 1 -

[0751] In formula (4-3), X 1 It preferably includes a structure in which two or more hydrogen atoms are removed from a structure represented by any one of the following formulae (V-1) to (V-4).

[0752] [Chemical Formula 21]

[0753]

[0754] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0755] In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R x2 With R X3 They can be bonded to form a ring structure.

[0756] In formula (V-2), R X1 Each independently is preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one of the hydrogen atoms of an alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

[0757] In formula (V-3), R X2 and R X3 Each of them is independently preferably a hydrogen atom.

[0758] In R X2 With R X3 When the ring structure is formed by bonding, RX2 With R X3 The structure formed by the bond is preferably a single bond, -O- or -CR2-, more preferably -O- or -CR2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

[0759] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents the same group as X in formula (4-3). 1 The bonding positions of the four bonded carbonyl groups, n1 represents an integer of 0 to 5, preferably an integer of 1 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms be substituted by R in the formula (4-3). 1 replace.

[0760] [Chemical Formula 22]

[0761]

[0762] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), X 1 The group represented by the following formula (V-2-1) or formula (V-2-2) is preferred. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. X1 represents a single bond or -O-, * represents the X in formula (4-3) 1 The bonding positions of the four carbonyl groups bonded. X1 The definition and preferred embodiment of are as described above. In addition, the hydrogen atoms in these structures may be further substituted by well-known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (4-3). 1 replace.

[0763] [Chemical Formula 23]

[0764]

[0765] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 1The group represented by the following formula (V-3-1) or formula (V-3-2) is preferred. From the viewpoint of reducing the dielectric constant, the group represented by formula (V-3-2) is preferred. In the following formula, * represents X in formula (4-3). 1 The bonding positions of the four carbonyl groups bonded. X2 and R X3 The definition and preferred embodiment of are as described above. In addition, the hydrogen atoms in these structures may be further substituted by well-known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (4-3). 1 replace.

[0766] [Chemical Formula 24]

[0767]

[0768] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), X 1 Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents the same group as X in formula (4-3). 1 The bonding positions of the four bonded carbonyl groups, n1 represents an integer from 0 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (4-3) is an integer from 1 to 4, it is preferred that m hydrogen atoms be substituted by R in the formula (4-3). 1 replace.

[0769] [Chemical Formula 25]

[0770]

[0771] In addition, X 1 It can be R in the above formula (4) 132 The group represented by is obtained by removing m hydrogen atoms.

[0772] And, X 1 It is preferred that the structure does not contain an imide structure.

[0773] In the present invention, the imide structure is a structure represented by -C(=O)N(-*)C(=O)-. * represents a bonding position to another structure.

[0774] And, X 1 It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0775] In the present invention, the urethane bond refers to the bond consisting of *-OC(=O)-NR N-* indicates a key, R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to the carbon atom. N It is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

[0776] In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N Each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding position to a carbon atom. N The preferred embodiment is as described above.

[0777] In the present invention, the amide bond is *-NR N -C(=O)-* represents a bond, R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to the carbon atom. N The preferred embodiment is as described above.

[0778] In addition, X 1 It is preferred that no ester bond be present in the structure.

[0779] In the present invention, the ester bond is a bond represented by *-OC(=O)-*.

[0780] Among these, X 1 It is preferable that the polyol contains no imide structure, urethane bond, urea bond, or amide bond, and it is preferable that the polyol contains no imide structure, urethane bond, urea bond, amide bond, or ester bond.

[0781] -Y 1 -

[0782] In formula (4-3), Y 1 It preferably contains a structure in which two or more hydrogen atoms are removed from the structure represented by any one of the above formulae (V-1) to (V-4).

[0783] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y 1 It is preferably a group formed by removing n hydrogen atoms from a group represented by the following formula (V-1-2). In the following formula, * represents Y in formula (4-3). 1 The bonding positions of the two nitrogen atoms bonded are represented by n1, which is an integer from 1 to 5. The number of hydrogen atoms in the following structure is represented by R in formula (4-3). 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in the following structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0784] [Chemical Formula 26]

[0785]

[0786] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y 1 The group represented by the following formula (V-2-3) or formula (V-2-4) is preferred. From the viewpoint of reducing the dielectric constant, the group represented by formula (V-2-4) is preferred. X1 represents a single bond or -O-, * represents the Y in formula (4-3) 1 The bonding position of the two nitrogen atoms bonded. X1 The preferred embodiment is as described above. The n hydrogen atoms in the following structure are represented by R in formula (4-3). 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0787] [Chemical Formula 27]

[0788]

[0789] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y 1 The group represented by the following formula (V-3-3) or formula (V-3-4) is preferred. From the viewpoint of reducing the dielectric constant, the group represented by formula (V-3-3) is preferred. In the following formula, * represents the same as Y in formula (4-3). 1 The bonding position of the two nitrogen atoms bonded. X2 and R X3 The preferred embodiment is as described above. The n hydrogen atoms in the following structure are represented by R in formula (4-3). 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0790] [Chemical Formula 28]

[0791]

[0792] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y 1The group represented by the following formula (V-4-2) is preferred. In the following formula, * represents the same as Y in formula (4-3). 1 The bonding positions of the two nitrogen atoms bonded are represented by n1, which is an integer from 0 to 5. In addition, the embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in the following structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0793] [Chemical Formula 29]

[0794]

[0795] In addition, Y 1 It can be R from the above formula (4) 131 The group represented by is obtained by removing n hydrogen atoms.

[0796] And, Y 1 It is preferred that the structure does not contain an imide structure.

[0797] And, Y 1 It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0798] In addition, Y 1 It is preferred that no ester bond be present in the structure.

[0799] Among these, Y 1 It preferably does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0800] Among these, X in formula (4-3) 1 and Y 1 It is preferable that each of the structures represented by any one of the above formulae (V-1) to (V-4) contain a structure in which two or more hydrogen atoms are removed.

[0801] In formula (4-3), m is an integer of 0 to 2, and more preferably 0 or 1. Furthermore, an embodiment in which m is 0 is also one of the preferred embodiments of the present invention.

[0802] In formula (4-3), n is preferably 1 or 2, more preferably 2.

[0803] The polyimide preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0804] To improve adhesion to the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0805] In order to improve the storage stability of the resin composition, the main chain ends of the polyimide are preferably blocked with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or an active monoester compound. Among these, monoamines are more preferably used. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0806] -Imidization rate (ring closure rate)-

[0807] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

[0808] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0809] The imidization rate can be measured, for example, by the following method.

[0810] Measure the infrared absorption spectrum of polyimide and find the absorption peak at 1377 cm-1 derived from the imide structure. -1 Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0811] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0812] Polyimide can contain repeating units with all R 131 and R 132 The repeating unit represented by the above formula (4) may also contain R 131 and R 132 The polyimide may contain two or more repeating units represented by the above formula (4) in combination with different repeating units. In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include repeating units represented by the following formula (2).

[0813] For example, polyimide can be obtained by reacting tetracarboxylic dianhydride with diamine (a portion of which is substituted with a monoamine, i.e., an end-capping agent) at low temperature, reacting tetracarboxylic dianhydride with diamine (a portion of which is substituted with an acid anhydride or a monoacyl chloride compound or an active monoester compound, i.e., an end-capping agent) at low temperature, reacting a diester by tetracarboxylic dianhydride and an alcohol in the presence of a diamine (a portion of which is substituted with a monoamine, i.e., an end-capping agent) and a condensing agent, chlorinating the remaining dicarboxylic acid after obtaining a diester by tetracarboxylic dianhydride and an alcohol and reacting it with a diamine (a portion of which is substituted with a monoamine, i.e., an end-capping agent), and the like, and then completely imidizing it by a conventional imidization reaction method or stopping the imidization reaction midway and introducing a portion of an imide structure, or synthesizing it by further mixing a completely imidized polymer and its polyimide precursor to introduce a portion of an imide structure. In addition, other known methods for synthesizing polyimides can also be applied.

[0814] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. A weight-average molecular weight of 5,000 or greater can improve the bending resistance of the cured film. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or greater is particularly preferred.

[0815] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0816] The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0817] When the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide be within the above ranges. It is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polyimides, calculated as a single resin, be within the above ranges.

[0818] [Polybenzoxazole precursor]

[0819] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but it preferably contains a repeating unit represented by the following formula (3).

[0820] [Chemical formula 30]

[0821]

[0822] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0823] In formula (3), R 123 and R 124 Respectively with R in formula (2) 113 , and the preferred range is also the same. That is, at least one is preferably a polymerizable group.

[0824] In formula (3), R 121 Represents a divalent organic group. As a divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As an aliphatic group, a straight-chain aliphatic group is preferred. R 121 A dicarboxylic acid residue is preferably used. Only one dicarboxylic acid residue may be used, or two or more dicarboxylic acid residues may be used.

[0825] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.

[0826] The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10 carbon atoms. The linear aliphatic group is preferably an alkylene group.

[0827] Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid Acid, behenedioic acid, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

[0828] [Chemical Formula 31]

[0829]

[0830] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0831] As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid consisting only of a group having the following aromatic group and two -COOH groups is more preferred.

[0832] [Chemical Formula 32]

[0833]

[0834] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * independently represents the bonding position to other structures.

[0835] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0836] In formula (3), R 122 represents a tetravalent organic group. As a tetravalent organic group, R 115 The meanings and preferred ranges are the same.

[0837] R122 Preferred are groups derived from bisaminophenol derivatives. Examples of the groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

[0838] Among the bisaminophenol derivatives, those having the following aromatic groups are preferred.

[0839] [Chemical Formula 33]

[0840]

[0841] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, * and # represent the bonding position with other structures respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. In addition, R 122 The structure represented by the above formula is also preferred. 122 In the case of the structure represented by the above formula, among the total of 4 * and #, it is preferred that any two of them are the same as R in formula (3). 122 The bonding position of the nitrogen atom to which the bond is attached and the other two are R in formula (3) 122 The bonding position of the oxygen atom to which the bond is attached is preferably 2*, which is the same as that of R in formula (3). 122 The bonding position of the oxygen atom to which the two # are bonded is the same as R in formula (3) 122 The bonding position of the nitrogen atom to which it is bonded, or 2 * are R in formula (3) 122 The bonding position of the nitrogen atom to which the two # are bonded is the same as R in formula (3) 122 The bonding position of the oxygen atom to which the bond is attached is preferably 2*, which is the same as R in formula (3).122 The bonding position of the oxygen atom to which the two # are bonded is the same as R in formula (3) 122 The bonding position of the bonded nitrogen atom.

[0842] The bisaminophenol derivative is also preferably a compound represented by formula (As).

[0843] [Chemical Formula 34]

[0844]

[0845] In formula (As), R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group represented by the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[0846] [Chemical Formula 35]

[0847]

[0848] In the organic group selected from the group represented by formula (A-sc), * represents a bond to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (As).

[0849] In formula (As), having a substituent at the ortho position to the phenolic hydroxyl group, i.e., R3, is particularly preferred because it is believed that this brings the carbonyl carbon of the amide bond and the hydroxyl group closer together and further enhances the cyclization rate during curing at low temperatures.

[0850] In the formula (As), when R2 and R3 are both alkyl groups, high transparency to i-rays and a high cyclization rate during curing at low temperatures can be maintained, which is preferred.

[0851] In formula (As), R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group represented by R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in terms of achieving a well-balanced polybenzoxazole precursor having sufficient solubility in a solvent while maintaining high transparency to i-rays and a high cyclization rate during curing at low temperatures.

[0852] As a method for producing the bisaminophenol derivative represented by formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506, the contents of which are incorporated herein.

[0853] Specific examples of the structure of the bisaminophenol derivative represented by formula (As) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated herein. Specific examples of the structure of the bisaminophenol derivative represented by formula (As) are not limited to these.

[0854] The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (3).

[0855] From the viewpoint of being able to suppress warpage caused by ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0856] [Chemical Formula 36]

[0857]

[0858] In formula (SL), Z has structures a and b, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s 、R 4s 、R 5s 、R 6s At least one of the groups is an aromatic group, and the remaining groups are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structures a and b may be block or random. Regarding the mole % of the Z portion, structure a is 5 to 95 mole %, structure b is 95 to 5 mole %, and a + b is 100 mole %.

[0859] In formula (SL), preferred Z includes R in structure b. 5s and R 6s The structure is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be more effectively reduced, and both the effect of suppressing warping and the effect of improving solvent solubility can be achieved.

[0860] When a diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include R in formula (2): 115 example.

[0861] The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0862] The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or greater, more preferably 1.5 or greater, and even more preferably 1.6 or greater. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0863] When the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferred that at least one of the polybenzoxazole precursors has a weight average molecular weight, number average molecular weight, and dispersity within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polybenzoxazole precursors, calculated as a single resin, each be within the above ranges.

[0864] Polybenzoxazole

[0865] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a free radical polymerizable group. Furthermore, the compound may be represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.

[0866] [Chemical Formula 37]

[0867]

[0868] In formula (X), R 133 Represents a divalent organic group, R 134 represents a tetravalent organic group.

[0869] When the polarity conversion group such as a polymerizable group or an acid-decomposable group is present, the polymerizable group or the acid-decomposable group may be located at R 133 and R 134At least one of them may be located at a terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

[0870] Formula (X-1)

[0871] [Chemical Formula 38]

[0872]

[0873] In formula (X-1), R 135 and R 136 At least one of them is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polymerizable group or an acid-decomposable group, it is an organic group. The other groups have the same meanings as in formula (X).

[0874] Formula (X-2)

[0875] [Chemical Formula 39]

[0876]

[0877] In formula (X-2), R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the rest are substituents. Other groups have the same meanings as in formula (X).

[0878] The polarity conversion group such as the polymerizable group or the acid-decomposable group has the same meaning as the polymerizable group described in the polymerizable group of the polyimide precursor.

[0879] R 133 represents a divalent organic group. Examples of the divalent organic group include aliphatic groups and aromatic groups. As specific examples, R in the formula (3) of the polybenzoxazole precursor can be cited. 121 Examples, preferably with R 121 same.

[0880] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R in the formula (3) of the polybenzoxazole precursor. 122 Examples, preferably with R 122 same.

[0881] For example, as R 122 The four bonds of the exemplified tetravalent organic group are bonded to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. 134 When it is the following organic group, the following structure is formed: In the following structure, * represents the bonding position to the nitrogen atom or oxygen atom in formula (X).

[0882] [Chemical Formula 40]

[0883]

[0884] The oxazolidation rate of the polybenzoxazole is preferably 85% or greater, more preferably 90% or greater. The upper limit is not particularly limited and may be 100%. An oxazolidation rate of 85% or greater minimizes film shrinkage caused by ring closure during oxazolidation by heating, effectively suppressing warping.

[0885] For example, the above-mentioned oxazolylation rate can be measured by the following method.

[0886] The infrared absorption spectrum of polybenzoxazole was measured to find the absorption peak at 1650 cm-1 derived from the amide structure of the precursor. -1 Next, using the peak intensity Q1 near 1490 cm -1 The polybenzoxazole was heat treated at 350°C for 1 hour and then the infrared absorption spectrum was measured again to determine the absorption intensity of the aromatic ring at 1650 cm -1 The peak intensity Q2 near 1490 cm -1 The absorption intensity of the aromatic ring observed nearby is normalized. Using the obtained standard values of the peak intensities Q1 and Q2, the oxazolylation rate of the polybenzoxazole can be determined according to the following formula.

[0887] Oxazolylation rate (%) = (standard value of peak intensity Q1 / standard value of peak intensity Q2) × 100

[0888] Polybenzoxazole may contain R 133 and R 134 The repeating unit of the above formula (X) may also contain R 133 and R 134 The polybenzoxazole may contain other types of repeating units in addition to the repeating units of the formula (X).

[0889] For example, a bisaminophenol derivative is reacted with a 133 A polybenzoxazole precursor is obtained by reacting a dicarboxylic acid or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids, and then oxazolidinone is formed by a conventional oxazolidinone reaction method to obtain polybenzoxazole.

[0890] In the case of dicarboxylic acids, active ester-type dicarboxylic acid derivatives prepared by reacting with 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to improve the reaction yield.

[0891] The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[0892] The number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0893] The molecular weight dispersion of the polybenzoxazole is preferably 1.4 or greater, more preferably 1.5 or greater, and even more preferably 1.6 or greater. The upper limit of the molecular weight dispersion of the polybenzoxazole is not particularly limited, and for example, is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0894] When the resin composition contains multiple polybenzoxazoles as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole be within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polybenzoxazoles, calculated as a single resin, be within the above ranges.

[0895] [Polyamide-imide precursor]

[0896] The polyamideimide precursor preferably includes a repeating unit represented by the following formula (PAI-2).

[0897] [Chemical Formula 41]

[0898]

[0899] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 Represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 represents a hydrogen atom or a monovalent organic group.

[0900] In formula (PAI-2), R 117Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, and groups in which two or more of these groups are linked via a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and groups in which two or more of these groups are combined via a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms, and groups in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0901] As the above-mentioned connecting group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these, more preferred are -O-, -S-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these.

[0902] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0903] The alkylene halide is preferably one having 1 to 20 carbon atoms, more preferably one having 1 to 10 carbon atoms, and even more preferably one having 1 to 4 carbon atoms. Examples of the halogen atom in the alkylene halide include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The alkylene halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but preferably all hydrogen atoms are substituted with halogen atoms. Preferred examples of alkylene halide include (ditrifluoromethyl)methylene.

[0904] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0905] And, R 117 It is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the halogenation, chlorination is preferred.

[0906] In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

[0907] Two of the three carboxyl groups of the tricarboxylic acid compound may be converted to acid anhydride.

[0908] Examples of the halogenated tricarboxylic acid compound used for producing the polyamideimide precursor include branched aliphatic, cycloaliphatic, and aromatic tricarboxylic acid compounds.

[0909] These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0910] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these groups are combined via a single bond or a linking group. More preferred is a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0911] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or a phenylene group.

[0912] These compounds may be compounds in which two carboxyl groups are anhydrified (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride chloride).

[0913] In formula (PAI-2), R 111 、A 2 、R 113 The meanings of are respectively the same as those of R in the above formula (2) 111 、A 2 、R 113 The meanings and preferences are the same.

[0914] The polyamideimide precursor may further comprise other repeating units.

[0915] Examples of other repeating units include a repeating unit represented by the above-mentioned formula (2) and a repeating unit represented by the following formula (PAI-1).

[0916] [Chemical Formula 42]

[0917]

[0918] In formula (PAI-1), R 116 represents a divalent organic group, R 111 It represents a divalent organic group.

[0919] In formula (PAI-1), R 116Examples include linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or groups obtained by linking two or more of these groups via a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups via a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms or groups obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0920] As the above-mentioned connecting group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these, more preferred are -O-, -S-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these.

[0921] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0922] The alkylene halide is preferably one having 1 to 20 carbon atoms, more preferably one having 1 to 10 carbon atoms, and even more preferably one having 1 to 4 carbon atoms. Examples of the halogen atom in the alkylene halide include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The alkylene halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but preferably all hydrogen atoms are substituted with halogen atoms. Preferred examples of alkylene halide include (ditrifluoromethyl)methylene.

[0923] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0924] And, R 116 It is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide.

[0925] In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.

[0926] The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, and is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0927] Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound that may be halogenated and is used for producing the polyamideimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds.

[0928] These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0929] Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group is preferred, and a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0930] Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, Fluorosebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, henodecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyldiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0931] Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups are halogenated among the specific examples of the dicarboxylic acid compound described above.

[0932] In formula (PAI-1), R 111 The meaning of is the same as that of R in the above formula (2) 111The meanings and preferences are the same.

[0933] Furthermore, it is also preferred that the polyamide-imide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0934] Furthermore, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0935] As one embodiment of the polyamide-imide precursor in the present invention, there can be mentioned an embodiment containing a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), and a repeating unit represented by formula (2). The total content of the above repeating units is preferably 50 mol% or more of the total repeating units, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamide-imide precursor excluding the terminal can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).

[0936] Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, there can be mentioned an embodiment containing a repeating unit represented by formula (PAI-2) and a repeating unit represented by formula (PAI-1). The total content of the above repeating units is preferably 50 mol% or more of the total repeating units, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamide-imide precursor excluding the terminal can be either a repeating unit represented by formula (PAI-2) or a repeating unit represented by formula (PAI-1).

[0937] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0938] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyamide-imide precursor is not particularly limited, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. When the resin composition includes a plurality of polyamide-imide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one polyamide-imide precursor are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated using the plurality of polyamide-imide precursors as one resin are within the above ranges.

[0939] [Polyamide-imide]

[0940] The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide or a polyamide-imide soluble in a developer mainly composed of an organic solvent.

[0941] In this specification, an alkali-soluble polyamide-imide refers to a polyamide-imide capable of dissolving 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the perspective of pattern formation, the polyamide-imide preferably dissolves 0.5 g or more, and more preferably dissolves 1.0 g or more. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less.

[0942] Furthermore, from the viewpoint of film strength and insulating properties of the obtained organic film, the polyamide-imide is preferably a polyamide-imide having a plurality of amide bonds and a plurality of imide structures in the main chain.

[0943] -Fluorine atom-

[0944] From the viewpoint of the film strength of the obtained organic film, the polyamideimide preferably has fluorine atoms.

[0945] For example, the fluorine atom is preferably contained in R 117 or R 111 , more preferably R is contained as a fluorinated alkyl group in the repeating unit represented by the formula (PAI-3) described later 117 or R 111 .

[0946] The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more and preferably 20% by mass or less.

[0947] -Ethylenically unsaturated bond-

[0948] From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.

[0949] The polyamideimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0950] The ethylenically unsaturated bond is preferably radically polymerizable.

[0951] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 , more preferably R is included in the repeating unit represented by the formula (PAI-3) described later as a group having an ethylenically unsaturated bond. 117 or R 111 .

[0952] Preferred embodiments of the group having an ethylenically unsaturated bond are the same as preferred embodiments of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0953] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamide-imide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0954] -Polymerizable groups other than ethylenically unsaturated bonds-

[0955] The polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.

[0956] Examples of the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same polymerizable groups other than the ethylenically unsaturated bond as those mentioned above in the polyimide.

[0957] For example, it is preferable that a polymerizable group other than an ethylenically unsaturated bond is contained in R in a repeating unit represented by the formula (PAI-3) described later. 111 .

[0958] The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamide-imide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0959] -Polarity conversion group-

[0960] The polyamide-imide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamide-imide and the R 113 and R 114 The acid-decomposable groups described in , and preferred embodiments are also the same.

[0961] -Acid value-

[0962] When polyamideimide is used for alkali development, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more, from the viewpoint of improving developability.

[0963] Furthermore, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0964] When polyamideimide is used for development using a developer containing an organic solvent as a main component (eg, "solvent development"), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0965] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0966] Furthermore, examples of the acid groups contained in the polyamide-imide include the same groups as those in the above-mentioned polyimide, and preferred embodiments are also the same.

[0967] -Phenolic hydroxyl group-

[0968] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

[0969] The polyamide-imide may have a phenolic hydroxyl group at a main chain terminal or a side chain.

[0970] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 .

[0971] The amount of the phenolic hydroxyl group relative to the total mass of the polyamide-imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0972] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

[0973] [Chemical Formula 43]

[0974]

[0975] In formula (PAI-3), R 111 and R 117Respectively with R in formula (PAI-2) 111 and R 117 The meanings and preferences are the same.

[0976] When there is a polymerizable group, the polymerizable group can be located at R 111 and R 117 It can also be located at at least one of the ends of the polyamide-imide.

[0977] Furthermore, to improve the storage stability of the resin composition, the main chain ends of the polyamide-imide are preferably capped with an end-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or an active monoester compound. Preferred embodiments of the end-capping agent are the same as those for the polyimide described above.

[0978] -Imidization rate (ring closure rate)-

[0979] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyamideimide is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

[0980] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0981] The imidization ratio is measured by the same method as the ring closure ratio of the polyimide.

[0982] Polyamide-imide may contain R 111 and R 117 The repeating unit represented by the above formula (PAI-3) may also contain R 111 and R 117 The polyamide-imide may further comprise a repeating unit of the formula (PAI-3) in combination of two or more different repeating units. In addition to the repeating unit represented by the formula (PAI-3), the polyamide-imide may also comprise other types of repeating units. Examples of other types of repeating units include repeating units represented by the formula (PAI-1) or the formula (PAI-2).

[0983] Polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it by a conventional imidization reaction method, or by stopping the imidization reaction midway and introducing a partial imide structure, or by further mixing a completely imidized polymer with the polyamideimide precursor to introduce a partial imide structure.

[0984] The weight-average molecular weight (Mw) of the polyamide-imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. A weight-average molecular weight of 5,000 or greater improves the bending resistance of the cured film. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or greater is particularly preferred.

[0985] Furthermore, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0986] The molecular weight dispersion of the polyamideimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyamideimide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0987] Furthermore, when the resin composition contains multiple polyamide-imides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyamide-imide be within the above-mentioned ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polyamide-imides, calculated as a single resin, be within the above-mentioned ranges.

[0988] [Method for producing polyimide precursor, etc.]

[0989] For example, polyimide precursors and the like can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain polyamic acid, and esterifying the obtained product with a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the obtained product in the presence of a diamine and a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the obtained product with a diamine, etc. Among the above production methods, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the obtained product with a diamine is more preferred.

[0990] Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0991] Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0992] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

[0993] In the method for producing a polyimide precursor, etc., it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds.

[0994] The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0995] In the method for producing a polyimide precursor, etc., it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0996] The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0997] -Capping agent-

[0998] In the manufacture method of polyimide precursor etc., in order to further improve storage stability, it is preferred to seal the carboxylic acid anhydride, anhydride derivative or amino group remaining in the resin end of polyimide precursor etc. When the carboxylic acid anhydride and anhydride derivative remaining in the resin end are end-blocked, as end-blocking agent, monoalcohol, phenol, mercaptan, thiophenol, monoamine etc. can be enumerated. From the perspective of reactivity and film stability, monoalcohol, phenols, monoamine are more preferably used. As the preferred compound of monoalcohol, methyl alcohol, ethanol, propyl alcohol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol and other primary alcohols, isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohol, tertiary alcohol, adamantane alcohol and other tertiary alcohols can be enumerated. As the preferred compound of phenols, phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene and other phenols can be enumerated. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a variety of different terminal groups may be introduced by reacting a variety of end-capping agents.

[0999] Moreover, when the amino group at the end of the resin is blocked, it is possible to block the end with a compound having a functional group that can react with the amino group. Preferred end-blocking agents for the amino group are preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic anhydride, sulfonic acid carboxylic anhydride, etc., more preferably carboxylic anhydride, carboxylic acid chloride. As preferred compounds of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be mentioned. And, as preferred compounds of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, valeryl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be mentioned.

[1000] -Solid precipitation-

[1001] In the manufacturing method of polyimide precursor etc., the process of solid precipitation can be included. Specifically, after filtering the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution as needed, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol or its mixed solution and the polymer component is precipitated, thereby making it precipitate as a solid and dry to obtain polyimide precursor etc. In order to improve the degree of purification, the polyimide precursor etc. can be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. The process of removing ionic impurities using an ion exchange resin can also be further included.

[1002] 〔content〕

[1003] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solids content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[1004] The resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[1005] It is also preferred that the resin composition of the present invention contains at least two resins.

[1006] Specifically, the resin composition of the present invention may contain two or more specific resins in total of the specific resin and other resins described below, or may contain two or more specific resins, and preferably contains two or more specific resins.

[1007] When the resin composition of the present invention contains two or more specific resins, for example, it is preferable to contain a structure derived from a dianhydride (R represented by the above formula (2)) which is a polyimide precursor. 115 ) Two or more different polyimide precursors.

[1008] <Other resins>

[1009] The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[1010] Examples of other resins include phenolic resins, polyamides, epoxy resins, silicones, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[1011] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coating properties can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.

[1012] For example, by replacing or adding to the polymerizable compound described below, a polymerizable group having a weight average molecular weight of 20,000 or less (for example, a polymerizable group having a molar content of 1×10 -3 mol / g or more) Adding a (meth)acrylic resin to the resin composition can improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), and the like.

[1013] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[1014] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[1015] As one preferred embodiment of the resin composition of the present invention, a method in which the content of other resins is low can also be used. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total solids content of the resin composition. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[1016] The resin composition of the present invention may contain only one other resin or two or more other resins. When containing two or more other resins, the total amount is preferably within the above range.

[1017] <Polymerizable Compound>

[1018] The resin composition of the present invention preferably contains a polymerizable compound.

[1019] Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[1020] 〔Free radical crosslinker〕

[1021] The resin composition of the present invention preferably contains a radical crosslinking agent.

[1022] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferably included. As the above-mentioned group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be mentioned.

[1023] Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[1024] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[1025] The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.

[1026] From the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[1027] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[1028] As the concrete example of free radical crosslinking agent, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) or its esters, amides can be enumerated, preferably the ester of unsaturated carboxylic acid and polyol compound and the amides of unsaturated carboxylic acid and polyamine compound.Also, it is also possible to preferably use the addition reaction product of unsaturated carboxylic acid ester or amides and monofunctional or polyfunctional isocyanates or epoxies with nucleophilic substituents such as hydroxyl, amino, thiol, and the dehydration condensation reaction product of monofunctional or polyfunctional carboxylic acid etc.Also, it is preferred to have the addition reaction product of unsaturated carboxylic acid ester or amides and monofunctional or polyfunctional alcohols, amines, thiols with the electrophilic substituents such as isocyanate group, epoxy group, and then also preferably have the substitution reaction product of unsaturated carboxylic acid ester or amides and monofunctional or polyfunctional alcohols, amines, thiols with the leaving property substituents such as halogen, p-toluenesulfonyloxy (tosyloXy group). Furthermore, as another example, the unsaturated carboxylic acid may be replaced with a compound group substituted with an unsaturated phosphonic acid, styrene, or a vinylbenzene derivative, vinyl ether, or allyl ether. Specific examples include reference to paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated herein by reference.

[1029] The radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher at normal pressure. Examples of compounds having a boiling point of 100° C. or higher at normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[1030] Preferred radical crosslinking agents other than those mentioned above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, and the contents are incorporated into this specification.

[1031] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. These oligomers can also be used.

[1032] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having four vinyloxy chains; SR-209, 231, and 239, bifunctional methacrylates having four vinyloxy chains (all manufactured by Sartomer Company, Inc.); DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains; TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.); urethane oligomers UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.); NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (all manufactured by Nippon Kayaku Co., Ltd.). Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[1033] Preferred free radical crosslinking agents include urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Application Laid-Open No. 62-039417, and Japanese Patent Application Laid-Open No. 62-039418. Free radical crosslinking agents also include compounds having an amino structure or a thioether structure in the molecule, as described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238.

[1034] The free radical crosslinking agent may be one having an acid group such as a carboxyl group or a phosphoric acid group. Preferred free radical crosslinking agents having an acid group are esters of aliphatic polyols and unsaturated carboxylic acids. More preferred free radical crosslinking agents are those obtained by reacting the unreacted hydroxyl groups of the aliphatic polyols with a non-aromatic carboxylic anhydride to impart acid groups. Particularly preferred are compounds obtained by reacting the unreacted hydroxyl groups of the aliphatic polyols with a non-aromatic carboxylic anhydride to impart acid groups, wherein the aliphatic polyol is pentaerythritol or dipentaerythritol. Examples of commercially available products include polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI Co., Ltd.

[1035] The acid value of the radical crosslinking agent containing an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. A radical crosslinking agent with an acid value within this range provides excellent workability and developability during production. Furthermore, the polymerizability is good. The acid value is measured in accordance with JIS K 0070:1992.

[1036] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from a urea bond and a urethane bond (hereinafter also referred to as “crosslinking agent U”) is also preferred.

[1037] In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N Each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding position to a carbon atom.

[1038] In the present invention, the urethane bond refers to the bond consisting of *-OC(=O)-NR N -* indicates a key, R Nrepresents a hydrogen atom or a monovalent organic group, and * represents a bonding position to a carbon atom.

[1039] When the resin composition contains the crosslinking agent U, chemical resistance, resolution, etc. may be improved.

[1040] The mechanism by which the above effects are achieved is not clear, but it is thought that, for example, a portion of the crosslinking agent U is thermally decomposed during curing by heating, etc., thereby generating amines, etc., which promote the cyclization of a precursor of a cyclized resin such as a polyimide precursor.

[1041] The crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have two or more urea bonds without a urethane bond, or may have two or more urethane bonds without a urea bond.

[1042] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[1043] When the crosslinking agent U does not have a urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[1044] When the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[1045] The free radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamide, vinylphenyl or maleimide, and more preferably (meth)acryloyloxy.

[1046] When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different.

[1047] The number of radical polymerizable groups in the crosslinking agent U may be only one or two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[1048] The radical polymerizable group value (mass of radical polymerizable groups per 1 mol of the compound) in the crosslinking agent U is preferably 150 to 400 g / mol.

[1049] From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[1050] From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[1051] The polymerizable group value of the crosslinking agent U is preferably 210 to 400 g / mol, more preferably 220 to 400 g / mol.

[1052] The crosslinking agent U preferably has a structure represented by the following formula (U-1), for example.

[1053] [Chemical Formula 44]

[1054]

[1055] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1 valent organic group, X is a radical polymerizable group, n is an integer of 1 or greater, and m is an integer of 1 or greater.

[1056] R U1 A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[1057] R N A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[1058] Z U1 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of

[1059] The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and further preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds of these groups. N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or a methyl group.

[1060] Z U2 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of

[1061] Examples of the hydrocarbon group include U1 The same groups as those mentioned above are also preferred in the same manner.

[1062] X is not particularly limited and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, and maleimide. Preferred are (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, and maleimide. More preferred are (meth)acryloyloxy.

[1063] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[1064] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[1065] The crosslinking agent U preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

[1066] From the viewpoint of chemical resistance of the obtained cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but is preferably an alcoholic hydroxyl group.

[1067] From the viewpoint of chemical resistance of the obtained cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, further preferably an alkyleneoxy group having 2 to 4 carbon atoms, further preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.

[1068] The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, more preferably 2 to 6.

[1069] Amide refers to -C(=O)-NR N - represents the bond. N As described above, when the crosslinking agent U has an amide group, the crosslinking agent U can contain an amide group as a N -* or a group represented by *-C(=O)-NR N - A group represented by R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[1070] The crosslinking agent U may have two or more structures selected from the group consisting of hydroxyl groups, alkyleneoxy groups (polyalkyleneoxy groups when forming polyalkyleneoxy groups), amide groups, and cyano groups in the molecule, but preferably has only one structure in the molecule.

[1071] The above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U. However, from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of the above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group is linked to at least one radical polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1").

[1072] In particular, when the crosslinking agent U contains only one free radical polymerizing group, it is preferred that the free radical polymerizing group contained in the crosslinking agent U is linked to at least one selected from a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").

[1073] When the crosslinking agent U contains an alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) is not particularly limited, and is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination of these. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferred, a hydrocarbon group having 18 or less carbon atoms is more preferred, and a hydrocarbon group having 16 or less carbon atoms is further preferred. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these can be cited. In addition, the preferred embodiment of the free radical polymerizable group is the same as the preferred embodiment of the free radical polymerizable group in the above-mentioned crosslinking agent U.

[1074] When the crosslinking agent U contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the amide group is not particularly limited, and is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination of these. As the above-mentioned hydrocarbon group, a hydrocarbon group with 20 or less carbon atoms is preferred, a hydrocarbon group with 18 or less carbon atoms is more preferred, and a hydrocarbon group with 16 or less carbon atoms is further preferred. In addition, as the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these can be cited. The preferred embodiment of the free radical polymerizable group is the same as the preferred embodiment of the free radical polymerizable group in the above-mentioned crosslinking agent U. In addition, in the above embodiment, the carbon atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2.

[1075] Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferred that the crosslinking agent U has a hydroxyl group.

[1076] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group.

[1077] The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferred that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[1078] The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may be a structure in which these groups form a condensed ring, but is preferably an aromatic hydrocarbon group.

[1079] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably a group formed by removing two or more hydrogen atoms from a benzene ring structure.

[1080] The aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings, such as indole and benzimidazole.

[1081] As the hetero atom contained in the aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred.

[1082] The aromatic group is preferably contained in a linking group that is linked to two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U.

[1083] The number of atoms (linked chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2-20, and even more preferably 2-10.

[1084] When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, in the case of containing two or more free radical polymerizable groups, or in the case of containing two or more urea bonds or urethane bonds and containing two or more free radical polymerizable groups, the minimum number of atoms among the number of atoms of the urea bond or urethane bond and the free radical polymerizable group (linked chain length) may be within the above range.

[1085] In this specification, the term "the number of atoms (chain length) between a urea bond or urethane bond and a polymerizable group" refers to the shortest (smallest) atomic chain connecting two atoms or groups of atoms to be linked. For example, in the structure represented by the following formula, the number of atoms (chain length) between the urea bond and the radically polymerizable group (methacryloyloxy group) is 2.

[1086] [Chemical Formula 45]

[1087]

[1088] 〔Axis of symmetry〕

[1089] The crosslinking agent U is also preferably a compound having a structure without an axis of symmetry.

[1090] Crosslinker U lacking an axis of symmetry means that the compound is bilaterally asymmetric and lacks an axis that would produce a molecule identical to the original molecule upon rotation of the entire compound. Furthermore, when noting the structural formula of crosslinker U on paper, "crosslinker U lacking an axis of symmetry" means that the structural formula of crosslinker U cannot be expressed as having an axis of symmetry.

[1091] Since the cross-linking agent U does not have a symmetric axis, it is considered that aggregation of the cross-linking agents U in the composition film is suppressed.

[1092] 〔Molecular weight〕

[1093] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and more preferably 200 to 900.

[1094] The method for producing the crosslinking agent U is not particularly limited, and the crosslinking agent U can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl group and an amino group.

[1095] The following are specific examples of the crosslinking agent U, but the crosslinking agent U is not limited thereto.

[1096] [Chemical Formula 46]

[1097]

[1098] [Chemical Formula 47]

[1099]

[1100] [Chemical Formula 48]

[1101]

[1102] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate in the resin composition.

[1103] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified dimethacrylate, in addition to these, bifunctional acrylates having a urethane bond, bifunctional methacrylates having a urethane bond can be used. These can be mixed and used in combination of two or more as needed.

[1104] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of approximately 200.

[1105] From the viewpoint of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a radical crosslinking agent. As a monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, mono(meth)acrylate polyethylene glycol, mono(meth)acrylate polypropylene glycol, (meth)acrylate derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other (meth) acrylic acid derivatives, allyl glycidyl ether. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, it is also preferred to use a compound having a boiling point of 100°C or more at normal pressure.

[1106] Examples of bifunctional or higher-functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[1107] When a free radical crosslinking agent is included, the content of the free radical crosslinking agent is preferably greater than 0% by mass and less than 60% by mass relative to the total solids content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[1108] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used simultaneously, the total amount thereof is preferably within the above range.

[1109] 〔Other crosslinking agents〕

[1110] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[1111] Other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents, and are preferably compounds having multiple groups in the molecule that accelerate the reaction (forming covalent bonds with other compounds in the composition or their reaction products) by exposure to light from a photoacid generator or a photobase generator, and more preferably compounds having multiple groups in the molecule that accelerate the reaction (forming covalent bonds with other compounds in the composition or their reaction products) by the action of an acid or a base.

[1112] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[1113] As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[1114] Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, acetylene carbamide, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atoms of the amino group are substituted with acyloxymethyl, hydroxymethyl, hydroxyethyl, or alkoxymethyl groups. The production methods of these compounds are not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. These compounds may also be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds.

[1115] As the above-mentioned amino-containing compound, a cross-linking agent using melamine is referred to as a melamine-based cross-linking agent, a cross-linking agent using acetylene carbamide, urea or alkylene urea is referred to as a urea-based cross-linking agent, a cross-linking agent using alkylene urea is referred to as an alkylene urea-based cross-linking agent, and a cross-linking agent using benzoguanamine is referred to as a benzoguanamine-based cross-linking agent.

[1116] Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[1117] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the following urea structure, or a triazine.

[1118] The alkoxymethyl group or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms.

[1119] The total number of alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[1120] The molecular weight of the compound is preferably 1500 or less, more preferably 180 to 1200.

[1121] [Chemical Formula 49]

[1122]

[1123] R 100 represents an alkyl group or an acyl group.

[1124] R 101 and R 102 Each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[1125] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula.

[1126] [Chemical Formula 50]

[1127]

[1128] In the formula, X represents a single bond or a divalent organic group, each R 104 Each independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that leaves by the action of an acid, a group consisting of -C(R4)2COOR 5 The group represented by (R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 It represents a group that leaves by the action of an acid.

[1129] R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[1130] Regarding the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that leaves by the action of an acid, the group consisting of -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[1131] Where R 36 ~R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[1132] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[1133] The alkyl group may be linear or branched.

[1134] The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

[1135] The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

[1136] The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[1137] The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.

[1138] The above-mentioned aralkyl group refers to an aryl group substituted by an alkyl group, and preferred embodiments of these alkyl groups and aryl groups are the same as preferred embodiments of the alkyl group and aryl groups.

[1139] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[1140] These groups may further have a known substituent.

[1141] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[1142] As the group that decomposes by the action of an acid to generate an alkali-soluble group or the group that leaves by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[1143] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. Preferred embodiments of the above compounds are the same as those for the crosslinking agent U, except that the polymerizable group is at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, and an alkoxymethyl group, rather than a radical polymerizable group.

[1144] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and a hydroxyethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds is replaced with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited thereto.

[1145] [Chemical Formula 51]

[1146]

[1147] [Chemical Formula 52]

[1148]

[1149] [Chemical Formula 53]

[1150]

[1151] As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product may be used, or a compound synthesized by a known method may be used.

[1152] From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[1153] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[1154] Specific examples of the urea-based crosslinking agent include monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxymethylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide.

[1155] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[1156] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea,

[1157] Propylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea,

[1158] 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[1159] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[1160] Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[1161] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenylhydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Benzophenone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[1162] As other cross-linking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

[1163] The resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[1164] -Epoxy compound (compound having an epoxy group)-

[1165] Epoxy compounds preferably have two or more epoxy groups per molecule. Epoxy groups undergo cross-linking reactions below 200°C and do not induce dehydration during cross-linking, thus minimizing film shrinkage. Therefore, the inclusion of epoxy compounds effectively suppresses low-temperature curing and warping of the resin composition.

[1166] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, preferably 2 to 15 repeating units.

[1167] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; silicones containing epoxy groups such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited to these. Specific examples include EPICLON (registered trademark, the same shall apply hereinafter) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON HP-4770, EPICLON EXA-830LVP, EPICLON EXA-8183, EPICLON EXA-8169, EPICLON N-660, EPICLON N-665-EXP-S, and EPICLON N-740 (these are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark, the same shall apply hereinafter) BEO-20E, RIKARESIN BEO-60E, RIKARESIN HBE-100, RIKARESIN DME-100, and RIKARESIN L-200 (these are trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark, hereinafter the same) 2021P, CELLOXIDE 2081, CELLOXIDE 2000, EHPE3150, EPOLEAD (registered trademark, hereinafter the same) GT401, EPOLEAD PB4700, EPOLEAD PB3600 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (these are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[1168] [Chemical Formula 54]

[1169]

[1170] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[1171] In the above structure, from the viewpoint of achieving both heat resistance and improvement in elongation, it is preferred that n is 1 to 2 and m is 3 to 7.

[1172] -Oxetane compound (compound having an oxetane group)-

[1173] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the ARON OXETANE series (e.g., OXT-121 and OXT-221) manufactured by TOAGOSEI CO., LTD. These compounds can be used alone or in combination of two or more.

[1174] -Benzoxazine compound (compound having a benzoxazolyl group)-

[1175] Benzoxazine compounds are preferred because they do not generate outgassing during curing due to a crosslinking reaction caused by a ring-opening addition reaction and also reduce thermal shrinkage to suppress the occurrence of warping.

[1176] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[1177] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solids content of the resin composition. The other crosslinking agent may be contained in a single species or in two or more species. When two or more other thermal crosslinking agents are contained, their total preferably falls within the above range.

[1178] The resin composition of the present invention preferably contains a photosensitizer.

[1179] Examples of the photosensitizer include polymerization initiators and photoacid generators.

[1180] 〔Polymerization initiator〕

[1181] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, and particularly preferably contains a photopolymerization initiator.

[1182] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active free radicals may be used.

[1183] The photoradical polymerization initiator preferably contains at least one having a photocatalytic activity of at least about 50 L·mol in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 cm -1 The molar absorptivity of a compound can be determined using known methods. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate as a solvent at a concentration of 0.01 g / L.

[1184] As a photoradical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. In addition, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent Application No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313. These contents are incorporated into this specification.

[1185] Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[1186] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents of these initiators are incorporated into this specification.

[1187] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[1188] As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[1189] As aminoacetophenone-based initiators, acylphosphine oxide-based initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. This content is incorporated into this specification.

[1190] Oxime compounds are more preferably used as photoradical polymerization initiators. Oxime compounds can further effectively improve exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[1191] Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Laid-Open No. 2000-066385, compounds described in Japanese Translation of PCT International Publication No. 2004-534797, compounds described in Japanese Patent Application Laid-Open No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application Laid-Open No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and the like, the contents of which are incorporated into this specification.

[1192] Preferred oxime compounds include, for example, compounds having the following structures: 3-(benzoyloxy(imino)butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. Oxime compounds serving as photoradical polymerization initiators have a linking group >C=NOC(=O)- in the molecule.

[1193] [Chemical Formula 55]

[1194]

[1195] Examples of commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, a photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by DaitoChemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds having the following structures can also be used.

[1196] [Chemical Formula 56]

[1197]

[1198] As the photoradical polymerization initiator, for example, oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189 can also be used.

[1199] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a substituent having a hydroxyl group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359 can also be used. These contents are incorporated into this specification.

[1200] As the photopolymerization initiator, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. OX1 As the aromatic ring group Ar OX1Examples of the electron-withdrawing group include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano groups. Acyl and nitro groups are preferred. From the perspective of ease of forming a film with excellent light resistance, acyl groups are more preferred, and benzoyl groups are even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclicoxy group, alkenyl, alkylsulfanyl, arylsulfanyl, acyl, or amino group. An alkyl, alkoxy, aryl, aryloxy, heterocyclicoxy group, alkylsulfanyl, arylsulfanyl, or amino group is more preferred. An alkoxy, alkylsulfanyl, or amino group is even more preferred.

[1201] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and more preferably a compound represented by the formula (OX2).

[1202] [Chemical Formula 57]

[1203]

[1204] Where R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group or a sulfamoyl group,

[1205] R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group,

[1206] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[1207] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[1208] In the above formula, preferably R X12 is an electron-withdrawing group and R X10 、R X11 、R X13 、R X14 A hydrogen atom.

[1209] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

[1210] Particularly preferred oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061, and the like, the contents of which are incorporated herein.

[1211] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[1212] Furthermore, the photoradical polymerization initiator is a trihalomethyl triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, and a benzophenone compound, further preferably a metallocene compound or an oxime compound.

[1213] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and the contents thereof are incorporated into this specification.

[1214] As the photoradical polymerization initiator, a photoradical polymerization initiator having difunctional or trifunctional functions or more can be used. By using this type of photoradical polymerization initiator, more than two free radicals are generated from a molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound of an asymmetric structure is used, crystallinity decreases and the solubility in a solvent etc. becomes higher, becomes difficult for precipitation over time, and thus can improve the time stability of resin combination. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds (E) and ( G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Unexamined Patent Application Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Unexamined Patent Application Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

[1215] When the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may be contained in a single species or in two or more species. When containing two or more photopolymerization initiators, the total amount is preferably within the above range.

[1216] In addition, a photopolymerization initiator may also function as a thermal polymerization initiator. Therefore, heating in an oven, hot plate, or the like may further promote crosslinking by the photopolymerization initiator.

[1217] 〔Sensitizer〕

[1218] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator or a photoradical polymerization initiator, electron transfer, energy transfer, and heat generation occur. This chemically changes the thermal radical polymerization initiator or the photoradical polymerization initiator, causing it to decompose and generate free radicals, acids, or bases.

[1219] As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oXonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[1220] Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamindanone, p-dimethylaminoindanone, and 4,4'-bis(dimethylamino)chalcone. Benzyl indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylv...

Claims

1. A component comprising: substrate; an insulating pattern disposed on the substrate; and a conductive pattern existing between the patterns of the insulating pattern, The difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate in the direction perpendicular to the substrate surface is 500 nm or less. An angle formed between a bottom surface of the conductive pattern and a side surface of the conductive pattern exceeds 90° and is equal to or less than 110°.

2. The component according to claim 1, wherein The conductive pattern is a line and space pattern, and a line width of the conductive pattern is greater than or equal to 0.1 μm and less than or equal to 10 μm.

3. The component according to claim 1 or 2, wherein The insulating pattern has an indentation elastic modulus of 6.0 GPa or less.

4. The component according to claim 1 or 2, wherein The insulating pattern includes polyimide.

5. The component according to claim 4, wherein The cyclization rate of the polyimide is greater than 70%.

6. The component according to claim 1 or 2, wherein The insulating pattern includes an ionic compound.

7. A component comprising: a substrate; a first insulating pattern on the substrate; a second insulating pattern on at least a portion of the surface of the first insulating pattern; and a conductive pattern for conducting electricity between a region between the first insulating patterns and a region between the second insulating patterns. The difference between the maximum and minimum values of the distance from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate in the direction perpendicular to the substrate surface of the component is 500 nm or less. An angle formed by a side surface of the conductive pattern in a region between a bottom surface of the conductive pattern and the second insulating pattern exceeds 90° and is equal to or less than 110°.

8. A method for manufacturing a component, the component comprising: substrate; Disposing an insulating pattern on the substrate; and a conductive pattern existing between the patterns of the insulating pattern, The method for manufacturing the component comprises: a conductive layer forming step of forming a conductive layer in regions between the insulating patterns of the substrate formed with the insulating patterns and on the insulating patterns to obtain component A; a grinding step of grinding the component A to obtain a component with the conductive pattern and the insulating pattern exposed on the surface; An angle formed between a bottom surface of the conductive pattern of the component and a side surface of the conductive pattern exceeds 90° and is equal to or less than 110°.

9. The method for manufacturing a component according to claim 8, wherein: Before the conductive layer forming step, A film forming process comprising the step of applying a composition for forming an insulating pattern on the substrate to form a film, The insulating pattern forming composition includes at least one compound selected from the group consisting of a photoradical generator and a photoacid generator.

10. The method for manufacturing a component according to claim 9, wherein: The insulating pattern forming composition has an i-ray transmittance of 5% or more when formed into a film having a thickness of 3 μm by heating at 100° C. for 3 minutes.

11. The method for manufacturing a component according to claim 9, wherein: After the film forming step, the method further comprises: a drying step of drying the film; an exposure step of exposing the dried film; and a developing step of developing the exposed film using a developer. The insulating pattern forming composition was applied on a silicon wafer and heated at 100° C. for 180 seconds at a concentration of 100 mJ / cm 2 The swelling rate of the film irradiated with i-rays at an irradiation dose of 1000 nm and heated at 110° C. for 3 minutes with respect to the developer was 15% by volume or less.

12. The method for manufacturing a component according to claim 9, wherein: After the film forming step, a heating step of heating the film at two or more heating temperatures is included.

13. A method for manufacturing a component, the component comprising: a substrate; a first insulating pattern present on the substrate; a second insulating pattern present on at least a portion of a surface of the first insulating pattern; and a conductive pattern for conducting electricity between a region between the first insulating patterns and a region between the second insulating patterns. The manufacturing method of the component includes steps A to C. The angle formed between the bottom surface of the conductive pattern of the component and the side surface of the conductive pattern exceeds 90° and is 110° or less, Step A: a step of preparing a component A including the first insulating pattern and the second insulating pattern; Step B: forming a conductive layer in the region between the first insulating patterns, the region between the second insulating patterns, and on the second insulating patterns of the component A to obtain a conductive layer forming step of component B; Step C: a step of polishing the component B to obtain a component in which the conductive pattern and the second insulating pattern are exposed. 14 . A photosensitive resin composition used for forming the insulating pattern in the manufacturing method according to claim 8 . The photosensitive resin composition according to claim 14 , comprising polyimide or a polyimide precursor.

16. A semiconductor component comprising the component according to claim 1, 2 or 7.

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