Methods for manufacturing permanent films, methods for manufacturing laminates and apparatus, and methods for manufacturing permanent films.

Abstract

The present invention provides a method for manufacturing a permanent film, a method for manufacturing a laminate comprising the method for manufacturing a permanent film, a method for manufacturing an apparatus comprising the method for manufacturing a permanent film or the method for manufacturing a laminate, and a permanent film obtained by the method for manufacturing a permanent film. The method for manufacturing a permanent film includes the steps of obtaining a substrate having a first pattern using a first resin composition, forming a second resin composition layer in at least one of the regions on and between the first pattern, and forming a second pattern, wherein the second resin composition includes a filler.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a permanent film, a method for manufacturing a laminate, a method for manufacturing an apparatus, and a permanent film. Prior Technology

[0002] In recent years, with the miniaturization of semiconductor devices, various resin compositions used to form patterns by means of photolithography or other methods for forming patterns using the aforementioned resin compositions have been explored during the manufacture of semiconductor devices.

[0003] For example, Patent Document 1 describes a dispersion solution containing filler, characterized in that a polyimide precursor solution composition is used to disperse the filler in a solvent.

[0004] Patent Document 2 describes a method for forming a low-dielectric-coefficient organic layer on a semiconductor substrate, characterized by a final nitrogen step performed 0 to 3 months prior to the initial curing step to remove water from the low-dielectric-coefficient organic layer. The method includes: forming a metal interconnect structure as a lower layer; performing the initial curing step on the low-dielectric-coefficient organic layer; and performing the final nitrogen step to remove water from the low-dielectric-coefficient organic layer.

[0005] [Patent Document 1] International Publication No. 2011 / 001949

[0006] [Patent Document 2] US Patent No. 6,403,464

[0007] When manufacturing devices, etc., when using resin compositions to form patterned permanent films, there are sometimes requirements for excellent adhesion between the obtained permanent film and the metal that comes into contact with it. Summary of the Invention

[0008] The purpose of this invention is to provide a method for manufacturing a permanent film that can achieve excellent adhesion to metals over a long period of time, a method for manufacturing a laminate that includes the method for manufacturing the permanent film, a method for manufacturing an apparatus that includes the method for manufacturing the permanent film or the method for manufacturing the laminate, and a permanent film obtained by the method for manufacturing the permanent film.

[0009] Examples of representative embodiments of the present invention are shown below.

[0010] <1> A method for manufacturing a permanent film includes the steps of: forming a first resin composition layer on a substrate using a first resin composition to obtain a substrate having a first pattern; applying a second resin composition to the substrate having the first pattern to form a second resin composition layer in at least one of the regions on and between the first pattern; and removing a portion of the second resin composition layer to form a second pattern in contact with the first pattern, wherein the second resin composition comprises a filler.

[0011] <2> like <1> In the method for manufacturing the permanent film, the area between the patterns in the composite pattern formed by the first pattern and the second pattern is narrower than the area between the patterns in the first pattern.

[0012] <3> like <1> or <2> In the method for manufacturing the permanent film, the filler included in the second resin composition is at least one filler selected from the group consisting of silicon dioxide, quartz, glass, ceramics, fluoropolymers and liquid crystal polymers.

[0013] <4> like <1> to <3> The method for manufacturing a permanent film according to any one of the claims, wherein the filler included in the second resin composition is at least one filler selected from the group consisting of hollow particles and porous particles.

[0014] <5> like <1> to <4> The method for manufacturing a permanent film according to any one of the claims, wherein the dielectric loss tangent of the filler is 0.01 or less.

[0015] <6> like <1> to <5> The method for manufacturing a permanent film according to any one of the claims, wherein the first resin composition is a negative photosensitive resin composition.

[0016] <7> like <1> to <6> The method for manufacturing a permanent film according to any one of the claims, wherein the step of obtaining a substrate having the first pattern is a step of selectively exposing the first resin composition layer and then developing it by solvent development.

[0017] <8> like <1> to <7> The method for manufacturing a permanent film according to any one of the claims, wherein the step of forming the second pattern is a step of removing a portion of the second resin composition layer by solvent development.

[0018] <9> like <1> to <8> The method for manufacturing a permanent film according to any one of the claims further includes a step of heating the first pattern and the second resin composition layer after the step of forming the second resin composition layer and before the step of forming the second pattern.

[0019] <10> like <1> to <9> The method for manufacturing a permanent film according to any one of the claims, wherein the second resin composition comprises a thermal polymerization initiator.

[0020] <11> like <1> to <10> The method for manufacturing a permanent film according to any one of the claims, wherein the second resin composition comprises a resin having a polymerizable group.

[0021] <12> like <1> to <11> The method for manufacturing a permanent film according to any one of the claims, wherein the resin included in the first resin composition is a polyimide precursor or a polyphenylene oxide precursor. Azole precursor.

[0022] <13> like <1> to <12> The method for manufacturing a permanent film according to any one of the claims, wherein the resin included in the second resin composition is a polyimide precursor or a polyphenylene oxide. Azole precursor.

[0023] <14> like <1> to <13> The method for manufacturing a permanent film according to any one of the claims, wherein the second resin composition comprises a polymeric compound having an aromatic group as a polymeric compound.

[0024] <15> like <1> to <14> A method for manufacturing a permanent film according to any one of the claims, wherein the obtained permanent film comprises polyimide or polyphenylene oxide. Azole.

[0025] <16> like <1> to <15> The method for manufacturing a permanent film according to any one of the claims, wherein the ratio of the coefficient of thermal expansion of the second pattern to the coefficient of thermal expansion of the first pattern is 60% or less.

[0026] <17> like <1> to <16> The method for manufacturing a permanent film according to any one of the above, wherein the first pattern includes at least one of a hole pattern and a groove pattern.

[0027] <18>A method for manufacturing a laminate, which includes the method for manufacturing a permanent film described in any one of <1> to <17>.

[0028] <19>A method for manufacturing a device, which includes the method for manufacturing a permanent film described in any one of <1> to <17> or the method for manufacturing a laminate described in <18>.

[0029] <20>A permanent film obtained by the method for manufacturing a permanent film described in any one of <1> to <17>. Brief Explanation of Drawings

[0030] FIG. 1 is a schematic diagram showing an example of the method for manufacturing a permanent film of the present invention.

[0031] FIG. 2 is a schematic cross-sectional view of a test carrier used in a biased HAST test. Summary of the Invention Problems to be Solved by the Invention

[0032] Means for Solving the Problems

[0033] Effects of the Invention

[0034] According to the present invention, there is provided a method for manufacturing a permanent film capable of obtaining a permanent film having excellent adhesion to a metal after a long time, a method for manufacturing a laminate including the method for manufacturing the permanent film, a method for manufacturing a device including the method for manufacturing the permanent film or the method for manufacturing the laminate, and a permanent film obtained by the method for manufacturing the permanent film. Brief Explanation of Drawings FIG. 1 is a schematic diagram showing an example of the method for manufacturing a permanent film of the present invention. FIG. 2 is a schematic cross-sectional view of a test carrier used in a biased HAST test. Embodiments

[0035] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments.

[0036] In this specification, a numerical range represented by the symbol "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively.

[0037] In this specification, the term "step" not only refers to an independent step, but also includes steps that cannot be clearly distinguished from other steps, as long as the intended function of the step can be achieved.

[0038] Regarding the designation of groups (atomic groups) in this specification, the designations for unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0039] 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. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation.

[0040] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acrylyl” means “acrylyl” and “methacrylyl” or either one.

[0041] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula.

[0042] In this specification, total solids content refers to the total mass of all components of the composition excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0043] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel permeation chromatography (GPC) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. Where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, the detection in GPC measurements shall be performed using a UV (ultraviolet) detector with a wavelength of 254 nm.

[0044] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the plurality of layers of interest. That is, a third layer or element may be further sandwiched between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Furthermore, unless otherwise specified, the direction of the gradually stacked layers relative to the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Moreover, this setting of up and down directions is for the convenience of explaining this specification; in actual practice, the "upper" direction in this specification may also differ from vertically upward.

[0045] In this specification, unless otherwise specified, each component included in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to that component.

[0046] Unless otherwise specified, the temperature in this instruction manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0047] In this specification, the combination of the better state sample is referred to as the superior state sample.

[0048] (Manufacturing method of permanent film)

[0049] The method for manufacturing a permanent film according to the present invention includes: a step of forming a first resin composition layer on a substrate using a first resin composition to obtain a substrate having a first pattern; a step of applying a second resin composition to the substrate having the first pattern to form a second resin composition layer in at least one of the regions on and between the first pattern; and a step of removing a portion of the second resin composition layer to form a second pattern in contact with the first pattern, wherein the second resin composition comprises a filler.

[0050] According to this manufacturing method, a second pattern containing filler is formed by contacting at least the first pattern.

[0051] It is believed that the CTE (coefficient of thermal expansion) of the second pattern containing filler is closer to that of a metal (e.g., a Cu electrode) than that of a pattern without filler.

[0052] Thus, in the composite pattern formed by the first pattern and the second pattern, a second pattern with CTE close to the metal is included between the first pattern and the metal. As a result, it is speculated that the difference between the deformation of the second pattern caused by heat and the deformation of the metal becomes smaller, so even after a long time, the delamination of the metal and the composite pattern can be suppressed.

[0053] In this invention, the condition that the metal and the pattern do not easily peel off even after a long period of time is also referred to as "high pattern reliability".

[0054] Furthermore, it is believed that when the first pattern does not contain filler or the filler content in the first pattern is less than the filler content in the second pattern, the elongation of the first pattern itself is greater than that of the pattern containing filler. Therefore, it is believed that when the above-mentioned composite pattern is formed and encapsulated, the first pattern functions as a material that alleviates mechanical stress. That is, for example, in a device, it is possible to achieve both the improved adhesion based on the second pattern and the alleviation of mechanical stress based on the first pattern.

[0055] Furthermore, when using resin compositions to form patterned permanent films included in devices such as semiconductor elements, there is a requirement to refine the shape of the obtained pattern (e.g., to form fine hole patterns or fine trench patterns).

[0056] In the past, patterns of resin compositions were formed by exposing and developing the resin composition in a patterned manner, or by forming a photoresist pattern on the resin composition and then using the photoresist pattern as a mask to etch the resin composition. However, due to the characteristics of the materials used and the limitations of the exposure wavelength used in the exposure, there are limits to the miniaturization of the patterns.

[0057] In this invention, for example, it is also possible to configure a composite pattern formed by the first pattern and the second pattern such that the area between the patterns is narrower than the area between the patterns in the first pattern. According to this configuration, compared with the case where only the first pattern is formed, it is possible to form fine patterns with small dimensions between the patterns.

[0058] That is, based on the above-mentioned pattern, the limit size of hole patterns, groove patterns, etc. can be reduced.

[0059] Furthermore, in addition to the reduced dimensions between the patterns, the thickness of the patterns themselves can also be increased compared to the case where only the first pattern is formed. Therefore, the aspect ratio of the patterns can also be increased.

[0060] Furthermore, with the miniaturization of patterns, the high integration of devices, the high frequency, and the miniaturization of devices, in order to suppress the increase of wiring resistance, suppress the decrease of permanent film resistance, and reduce propagation delay, it is required that the dielectric constant of permanent film (e.g., interlayer insulating film) be reduced.

[0061] When using a filler with a relatively low dielectric constant as the filler in the second resin composition of this invention, the dielectric constant of the second pattern in the permanent film (composite pattern) can also be reduced. As a result, it is speculated that: since the dielectric constant of the permanent film is lowered, propagation delay can also be reduced; and by reducing the dielectric constant of the permanent film, the inflow (migration) of metal ions from metals in wiring can be suppressed into the permanent film, thereby suppressing the increase in wiring resistance and reducing the resistance of the permanent film.

[0062] Furthermore, by including a resin with polymerizable groups in the first resin composition and a component with polymerizable groups (such as a resin with polymerizable groups or a polymeric compound) in the second resin composition, the reliability of the pattern can also be improved. In the above-described embodiments, it is believed that using resin compositions containing the same resin as the first and second resin compositions also helps to improve reliability.

[0063] In Patent Documents 1 and 2, the following configuration is not described: a step of forming a second resin composition layer in at least one of the regions on and between the first pattern, and a step of removing a portion of the second resin composition layer to form a second pattern in contact with the first pattern, wherein the second resin composition comprises a filler.

[0064] An example of a method for manufacturing the permanent film of the present invention is shown in FIG1.

[0065] Figure 1(a) shows an example of a substrate having a first pattern 2 on a substrate 1.

[0066] In Figure 1(a), a first pattern 2 is formed on the substrate 1, and a pattern-interval region 4 (a region where no pattern exists) is formed between the two first patterns.

[0067] Figure 1(b) shows an example of a state in which a second resin composition layer is formed on the first pattern and in the area between the first patterns.

[0068] In Figure 1(b), the second resin composition layer 6 is formed on the first pattern 2 and in the region 4 between the patterns.

[0069] In Figure 1(b), a second resin composition layer is formed in both the first pattern and the region between the first patterns. However, in this invention, it is sufficient for the second resin composition layer to be formed in at least one of the regions 4 between the first pattern 2 and the region 4 between the first pattern 2.

[0070] Figure 1(c) shows the region 8 of the second resin composition layer that was removed when a portion of the second resin composition layer shown in Figure 1(b) was removed. The region 8 that was removed is the area outside the dashed line in Figure 1(c) (the side opposite to the side of the second resin composition layer 6 that contacts the first pattern 2). The removal method will be described later.

[0071] Figure 1(d) shows an example of a state where a portion of the second resin composition layer has been removed.

[0072] The aforementioned region 8 in Figure 1(c) is removed, and a composite pattern formed by the first pattern 2 and the second pattern 10 is formed in Figure 1(d).

[0073] In Figure 1(d), for convenience, the first pattern 2 and the second pattern 10 are distinguished, but they can be formed into one by means of the covalent bonds of the components contained in each pattern.

[0074] In the case where a metal layer is formed in the region 12 between the patterns of the composite pattern or on the composite pattern, the metal layer is in contact with the second pattern 10 in the composite pattern. The second pattern 10 contains filler, and therefore it is considered that the CTE (coefficient of thermal expansion) of the second pattern 10 is closer to the CTE of the metal (e.g., Cu electrode) than that of the first pattern 2.

[0075] Therefore, as mentioned above, it is speculated that the delamination of the metal and the composite pattern can be suppressed even after a long period of time.

[0076] Furthermore, in this type of pattern, the area 12 between the patterns in the composite pattern in Figure 1(d) is narrower than the area 4 between the patterns in Figure 1(a).

[0077] Thus, the method for manufacturing a permanent film according to the present invention can narrow the area between patterns compared to the case where a pattern is formed solely from a first pattern. That is, it is possible to form fine patterns.

[0078] The steps included in the method for manufacturing the permanent film of the present invention will be described in detail below.

[0079] <Steps for forming the first pattern>

[0080] The method for manufacturing the permanent film of the present invention includes the step of forming a layer of the first resin composition on a substrate using a first resin composition to obtain a substrate having a first pattern (also referred to as the "first pattern forming step").

[0081] The details of the first resin composition will be described later.

[0082] The first pattern forming step preferably includes a first layer forming step of applying the first resin composition to a substrate to form a first resin composition layer.

[0083] Furthermore, it is preferable that the first pattern forming step includes the aforementioned first layer forming step, the first exposure step of selectively exposing the layer formed by the first layer forming step, and the first developing step of developing the layer exposed by the first exposure step with a developer to form a pattern.

[0084] The step of obtaining the substrate having the first pattern is preferably a step of selectively exposing the first resin composition layer and then developing it by solvent development. Solvent development refers to development using a developer containing an organic solvent, as described later.

[0085] That is, it is preferable that the first resin composition layer is a photosensitive layer for exposure and development, and it is preferable that it is a photosensitive layer for exposure and development using a developer containing organic solvents.

[0086] Furthermore, the first resin composition layer can be a photosensitive layer for positive development (hereinafter also referred to as "positive photosensitive layer") or a photosensitive layer for negative development, but it is preferable to use a photosensitive layer for negative development (hereinafter also referred to as "negative photosensitive layer").

[0087] In this invention, negative development refers to the development that removes the non-exposed areas by development, while positive development refers to the development that removes the exposed areas by development.

[0088] Furthermore, the first pattern forming step preferably includes at least one of the above-mentioned first layer forming step, the above-mentioned first exposure step, the above-mentioned first development step, the first heating step for heating the pattern obtained by the first development step, and the first post-development exposure step for exposing the pattern obtained by the development step.

[0089] Furthermore, it is preferable that the first pattern includes at least one of a hole pattern (e.g., a Via pattern) and a groove pattern.

[0090] Examples of hole patterns include those with diameters of 0.5 to 100 μm, with those of 3 to 50 μm being more preferred. Furthermore, the shape of the hole is not particularly limited; for example, a hole pattern that appears circular when viewed from above can be considered. In the case of a circular hole, the diameter of the hole pattern represents the diameter of the circle. In the case where the shape is not circular, the diameter of the hole pattern represents the diameter of the equivalent circle when viewed from above (the diameter of a circle with the same area as a shape having a certain area).

[0091] For example, groove patterns with a groove width of 0.5 to 100 μm can be cited, and groove patterns with a groove width of 3 to 50 μm are preferred.

[0092] The thickness of the first pattern is preferably 1~50μm, more preferably 2~20μm, and even more preferably 3~15μm.

[0093] [Steps for forming the first layer]

[0094] The method for manufacturing the permanent film of the present invention preferably includes the step of forming a first layer by applying a first resin composition onto a substrate.

[0095] -Substrate-

[0096] The type of substrate can be appropriately selected according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, any of the substrates formed of metal and substrates with metal layers formed by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred.

[0097] Furthermore, layers such as a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) may be provided on the surface of such substrates.

[0098] Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular.

[0099] For the dimensions of the substrate, if it is circular, the diameter is, for example, 100~450mm, preferably 200~450mm. If it is rectangular, the length of the shorter side is, for example, 100~1000mm, preferably 200~700mm.

[0100] Furthermore, as a substrate, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0101] Furthermore, when a layer is formed by applying the first resin composition to the surface of a resin layer (e.g., a layer formed by curing a resin composition) or a metal layer, the resin layer or the metal layer becomes a substrate.

[0102] Coating is a preferred method for applying the first resin composition to a substrate.

[0103] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of uniform layer thickness, spin coating, slot coating, spray coating, or inkjet coating are preferred. From the viewpoints of uniform layer thickness and productivity, spin coating and slot coating are better. By adjusting the solid content concentration of the first resin composition or the coating conditions according to the method, a layer of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0104] Furthermore, it can also be applied to the method of transferring a coating formed by pre-applying it to a dummy support using the above-mentioned application method onto a substrate.

[0105] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferred in this invention.

[0106] Furthermore, a step can be performed to remove excess layers at the ends of the substrate. Examples of such steps include edge bead rinsing (EBR) and back rinse.

[0107] Alternatively, a pre-wetting step can be used, in which various solvents are applied to the substrate to improve its wettability before the first resin composition is applied to the substrate.

[0108] [First drying step]

[0109] After the first layer formation step (after applying the first resin composition to the substrate), the first resin composition layer can be used in the step of drying the formed layer (first drying step) to remove solvent.

[0110] That is, the first pattern forming step may include a first drying step, which dries the first resin composition layer formed by the first layer forming step.

[0111] Furthermore, it is preferable that the first drying step is performed after the first layer formation step and before the first exposure step.

[0112] The drying temperature of the first resin composition layer in the first drying step is preferably 50~150℃, more preferably 70℃~130℃, and even more preferably 90℃~110℃. Alternatively, drying can be performed by reduced pressure. For drying time, examples include 30 seconds to 20 minutes, 1 minute to 10 minutes, and 2 minutes to 7 minutes, which are preferred.

[0113] [First exposure step]

[0114] The method for manufacturing the permanent film of the present invention preferably includes a first exposure step, wherein the first exposure step selectively exposes the first resin composition layer formed by the first layer forming step.

[0115] Selective exposure means exposing only a portion of a layer. Furthermore, selective exposure creates exposed areas (exposed portions) and unexposed areas (unexposed portions) on the layer.

[0116] Regarding the exposure amount, there are no special requirements as long as it can sensitize the first resin component. For example, an exposure energy of 50~10,000mJ / cm2 at a wavelength of 365nm is preferred, and 200~8,000mJ / cm2 is even better.

[0117] The exposure wavelength can be appropriately set within the range of 190~1,000nm, with 240~550nm being the optimal range.

[0118] Regarding the exposure wavelength, if explained in relation to the light source, examples include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), and wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet (EUV) (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. Among these, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is even better. This allows for particularly high exposure sensitivity.

[0119] Furthermore, there are no particular limitations on the exposure method, as long as it exposes at least a portion of the first resin composition layer. However, examples include exposure using a photomask and exposure based on direct laser imaging.

[0120] [Heating step after first exposure]

[0121] The first resin composition layer described above can be used in the step of heating after exposure (the first post-exposure heating step).

[0122] That is, the method for manufacturing the permanent film of the present invention may include a first post-exposure heating step, which heats the first resin composition layer exposed by the first exposure step.

[0123] The first post-exposure heating step can be performed after the first exposure step and before the first development step.

[0124] The heating temperature in the first exposure heating step is preferably 50℃~140℃, and even better is 60℃~120℃.

[0125] The heating time in the first exposure heating step is preferably 30 seconds to 300 minutes, and even better if it is 1 minute to 10 minutes.

[0126] Regarding the heating rate in the first exposure heating step, a rate of 1~12℃ / min from the initial heating temperature to the maximum heating temperature is preferred, 2~10℃ / min is even better, and 3~10℃ / min is further preferred.

[0127] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0128] There are no particular limitations on the heating mechanism used in the heating step after the first exposure; known heating plates, ovens, infrared heaters, etc., can be used.

[0129] Furthermore, it is also better to conduct the process in a low-oxygen environment by allowing inactive gases such as nitrogen, helium, and argon to flow through during heating.

[0130] [First developing step]

[0131] The first resin composition layer after exposure can be used in the first development step to form a pattern by developing with a developer.

[0132] That is, the method for manufacturing the permanent film of the present invention may include a first developing step, in which a developing solution is used to develop the first resin composition layer exposed by the first exposure step to form a pattern. By developing, one of the exposed and unexposed portions of the layer is removed, and a pattern is formed.

[0133] The development of the non-exposed portion of the layer that is removed by the development step is called negative development, and the development of the exposed portion of the layer that is removed by the development step is called positive development.

[0134] -Developer-

[0135] Examples of developers used in the first developing step include alkaline aqueous solutions or developers containing organic solvents.

[0136] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, 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 (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, with TMAH being more preferred. For example, when using TMAH, the content of alkaline compounds 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.

[0137] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3- Methyl alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate) Esters, such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ethers, etc. Ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., are preferred examples; as cyclic hydrocarbons, such as aromatic hydrocarbons like toluene, xylene, and anisole, and cyclic terpenes like limonene are preferred examples; as sulfoxides, such as dimethyl sulfoxide is preferred examples; as alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferred examples; and as amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylmethamide are preferred examples.

[0138] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, it is particularly preferred that the developer contains at least one solvent selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developer contains at least one solvent selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and the developer containing cyclopentanone is the most preferred.

[0139] When the developer contains organic solvents, it is preferable that the organic solvent content is 50% by mass or more relative to the total mass of the developer, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can be 100% by mass.

[0140] The developer may further contain other ingredients.

[0141] Other components include, for example, well-known surfactants and well-known defoamers.

[0142] -Developer supply method-

[0143] Regarding the method of supplying the developer, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the layered substrate in the developer, using a nozzle to supply the developer to the layer formed on the substrate for swirling immersion development, or continuously supplying the developer. There are no particular limitations on the type of nozzle, and examples include straight nozzles, spray nozzles, and mist nozzles.

[0144] From the perspectives of developer penetration, non-image area removal, and manufacturing efficiency, the method of supplying developer using a straight nozzle or a continuous supply method using a spray nozzle is preferable. From the perspective of developer penetration into the image area, the method of supplying using a spray nozzle is even better.

[0145] Alternatively, after continuously supplying developer using a straight nozzle, the substrate can be rotated to remove the developer from the substrate. After rotation drying, the substrate can be continuously supplied again using a straight nozzle, and the substrate can be rotated to remove the developer from the substrate. This process can be repeated several times.

[0146] Furthermore, as a method for supplying the developer in the developing step, steps such as continuously supplying the developer to the substrate, keeping the developer in a substantially static state on the substrate, vibrating the developer on the substrate using ultrasound or the like, and combinations thereof can be employed.

[0147] The optimal development time is 10 seconds to 10 minutes, with 20 seconds to 5 minutes being even better. There are no specific requirements for the temperature of the developing solution during development, but it is best performed at 10 to 45°C, and even better at 18 to 30°C.

[0148] In the developing step, after treatment with the developer, the pattern can be further cleaned (rinsed) using the rinsing solution. Alternatively, the rinsing solution can be supplied before the developer in contact with the pattern has completely dried.

[0149] -Flushing solution-

[0150] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. 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 rinsing solution.

[0151] When the rinsing solution contains an organic solvent, the organic solvent, preferably an ester, includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, alkyl 3-alkoxypropionate, etc.)). Ethyl 2-alkoxypropionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, etc. Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., are preferred examples, as well as... Cyclic hydrocarbons, such as aromatic hydrocarbons like toluene, xylene, and anisole, cyclic terpenes like limonene, sulfoxides like dimethyl sulfoxide, alcohols like methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and acetamides like N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide, etc.

[0152] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are further preferred.

[0153] When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of an organic solvent, more preferably 70% or more by mass of an organic solvent, and even more preferably 90% or more by mass of an organic solvent. Alternatively, the rinsing solution may contain 100% by mass of an organic solvent.

[0154] The rinsing solution may further contain other ingredients.

[0155] Other components include, for example, well-known surfactants and well-known defoamers.

[0156] -Method for supplying flushing fluid-

[0157] Regarding the method of supplying the rinsing fluid, there are no particular restrictions as long as the desired pattern can be formed. There are methods such as immersing the substrate in the rinsing fluid, supplying the rinsing fluid to the substrate based on a liquid coating method, supplying the rinsing fluid to the substrate in the form of a spray, and continuously supplying the rinsing fluid to the substrate through a mechanism such as a straight nozzle.

[0158] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, there are methods for supplying the rinsing fluid, such as spray nozzles, straight nozzles, and mist nozzles. Continuous supply using a mist nozzle is preferable, and from the perspective of the rinsing fluid's penetration into the image area, supplying via a mist nozzle is even better. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles.

[0159] That is, it is preferable to supply the rinsing solution to the developed pattern by means of a straight nozzle or by means of a continuous supply, and it is even better to supply the rinsing solution by means of a spray nozzle.

[0160] Furthermore, as a method for supplying the rinsing fluid in the rinsing step, steps such as continuously supplying the rinsing fluid to the substrate, keeping the rinsing fluid in a substantially static state on the substrate, vibrating the rinsing fluid on the substrate using ultrasound or the like, and combinations thereof can be employed.

[0161] For rinsing time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is even better. There is no particular requirement for the temperature of the rinsing solution, but it is best to perform the rinsing at 10 to 45°C, and even better at 18 to 30°C.

[0162] [First heating step]

[0163] The pattern obtained by the first developing step (or the washed pattern in the case of a rinsing step) can be used in the first heating step of heating the pattern obtained by the above developing step.

[0164] That is, the method for manufacturing the permanent film of the present invention may include a first heating step, which heats the pattern obtained by the first developing step.

[0165] Furthermore, the method for manufacturing the permanent film of the present invention may include a first heating step, which heats a pattern obtained by other methods without a development step or a first resin composition layer obtained by a first layer forming step.

[0166] The heating temperature (maximum heating temperature) in the first heating step is preferably 50~200℃, even better is 60~160℃, further better is 70~150℃, even more better is 80~140℃, and best is 90~120℃.

[0167] Regarding the heating in the first heating step, it is preferable to increase the temperature at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. A heating rate of 2 to 10°C / minute is more preferred, and 3 to 10°C / minute is even more preferred. By setting the heating rate to 1°C / minute or higher, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C / minute or lower, residual stress in the hardened material can be mitigated.

[0168] In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the initial 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.

[0169] A starting temperature of 20-120°C is preferred, 20-100°C is more preferred, and 20-80°C is even more preferred. The starting temperature refers to the temperature at which the heating process begins and reaches the maximum heating temperature. For example, the starting temperature could be the temperature of the layer after development (or rinsing), and it is preferable to begin heating from a temperature 30-200°C lower than the boiling point of the solvent contained in the first resin composition.

[0170] The heating time (heating time at the highest heating temperature) is preferably 30 seconds to 120 minutes, more preferably 60 seconds to 60 minutes, and even more preferably 90 seconds to 30 minutes.

[0171] Heating can be carried out in stages. Then, cooling can be performed after heating, with a cooling rate of 1-5°C / minute being optimal.

[0172] In terms of preventing the decomposition of specific resins, it is preferable to conduct the heating step in a low-oxygen environment by passing inert gases such as nitrogen, helium, or argon through the gas during the first heating step and by conducting the process under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even more preferred.

[0173] There are no particular limitations on the heating mechanism used in the first heating step; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0174] [First exposure step after development]

[0175] The pattern obtained by the first developing step (or the washed pattern in the case of a washing step) in addition to the first heating step described above or other than the first heating step described above can also be used in the first post-developing exposure step of the pattern after the exposure and developing step.

[0176] That is, the method for manufacturing the permanent film of the present invention may include a first post-development exposure step, wherein the first post-development exposure step exposes the pattern obtained by the first development step. The method for manufacturing the permanent film of the present invention may include a first heating step and a first post-development exposure step, or may include only one of the first heating step and the first post-development exposure step.

[0177] In the first exposure step after development, for example, it can promote the cyclization reaction of polyimide precursors by photosensitization by photoalkali generating agents or the removal of acid decomposition groups by photosensitization by photoacid generating agents.

[0178] In the first post-development exposure step, it is sufficient to expose at least a portion of the pattern obtained in the first development step, but it is preferable to expose the entire pattern.

[0179] The exposure amount in the first post-development exposure step is preferably 50~20,000 mJ / cm2, and even better if the exposure energy is converted to the wavelength at which the photosensitive compound is sensitive.

[0180] The first exposure step after development can be performed using the light source described in the first exposure step above, with broadband light being preferable.

[0181] [Pattern formation steps based on etching]

[0182] Furthermore, the first pattern forming step is preferably the following: after the first layer forming step, other layer forming steps are included, and the layer obtained by the other layer forming steps is exposed and developed to pattern it, and then the first pattern is formed by etching the above pattern as a mask.

[0183] As a method for patterning a layer obtained by other layer formation steps, such as by exposure and development, methods identical to the first exposure step and the first development step described above can be cited.

[0184] For etching, you can refer to well-known methods.

[0185] The etching process can be either dry etching or wet etching, but dry etching is preferred.

[0186] Furthermore, through the above etching, the pattern used as the mask can remain or be removed, but removal is preferable.

[0187] <Steps for forming the second layer>

[0188] The method for manufacturing the permanent film of the present invention includes the steps of applying a second resin composition to a substrate having the first pattern described above, and forming a second resin composition layer in at least one of the regions on the first pattern and between the first patterns (the second layer forming step).

[0189] Aside from the viewpoint of applying the second resin composition to a substrate having the first pattern, the second layer forming step can be performed using the same method as the first layer forming step. Furthermore, the second drying step may include the same drying step as the first drying step.

[0190] In the second layer forming step, the second resin composition layer can be formed, for example, on the entire surface of the substrate and the first pattern. Alternatively, the second resin composition layer can be formed only on a portion of the substrate and the first pattern.

[0191] The thickness of the second resin composition layer formed in the second layer formation step (the thickness of the layer formed on the first pattern) is preferably 0.1~20μm, and more preferably 1~10μm.

[0192] <Steps for forming the second pattern>

[0193] The method for manufacturing the permanent film of the present invention includes the step of removing a portion of the second resin composition layer to form a second pattern that contacts the first pattern.

[0194] The second pattern only needs to contact at least a portion of the first pattern, but it is preferable to form it so as to at least cover the side of the first pattern. Alternatively, the second pattern can be formed on all sides of the first pattern, or it can be formed on only a portion of the sides present on the first pattern.

[0195] Furthermore, it is preferable to form the second pattern so as to at least cover the upper surface of the first pattern. Also, the second pattern may be formed on all the upper surfaces of the first pattern, or it may be formed on only a portion of the upper surfaces of the plurality of upper surfaces present on the first pattern.

[0196] Furthermore, from the perspective of increasing the aspect ratio, it is also better to form a shape that covers the upper surface and sides of the first pattern.

[0197] When removing the second resin composition layer, it is preferable to remove it until a portion of the substrate is exposed. That is, it is preferable that the area where the second resin composition layer is removed includes at least the area where the first pattern is not present.

[0198] In this invention, the pattern formed by the second pattern and the first pattern is also referred to as a composite pattern.

[0199] It is preferable that the area between the patterns in the composite pattern formed by the first pattern and the second pattern is narrower than the area between the patterns in the first pattern.

[0200] The shape of the composite pattern is not particularly limited; for example, hole patterns (e.g., Via patterns) and groove patterns can be used.

[0201] It is preferable that the shape of the composite pattern is the same as that of the first pattern, except that the area between the patterns is narrowed. For example, in this invention, a composite pattern with the same shape as the first pattern can be formed, except that the area between the patterns is narrowed by performing a second preheating step and a developing step (and a second postheating step if necessary).

[0202] For example, when the first pattern is a hole pattern, it is preferable that the composite pattern is a hole pattern with a diameter smaller than that of the first pattern. Specifically, it is preferable that the diameter of the composite pattern as a hole pattern is reduced by 0.1 μm or more relative to the diameter of the first pattern as a hole pattern, more preferably by 0.3 μm or more, and even more preferably by 0.5 μm or more.

[0203] When the composite pattern is a hole pattern, examples include hole patterns with diameters of 0.5 to 100 μm, with hole patterns with diameters of 3 to 50 μm being preferred. The definition of the diameter of the hole pattern is as described above.

[0204] When the first pattern is a groove pattern, it is preferable that the composite pattern is a groove pattern with a groove width smaller than that of the first pattern. Specifically, it is preferable that the groove width of the composite pattern as a groove pattern is reduced by 0.1 μm or more relative to the groove width of the first pattern as a groove pattern, more preferably by 0.3 μm or more, and even more preferably by 0.5 μm or more.

[0205] When the composite pattern is a groove pattern, groove patterns with a groove width of 0.5~100μm can be cited as examples, and groove patterns with a groove width of 3~50μm are preferred.

[0206] [Second exposure step]

[0207] The second patterning step may include a second exposure step of exposing the second resin composition layer.

[0208] In the second exposure step, the entire surface of the second resin composition layer can be exposed, or a portion of the second resin composition layer can be selectively exposed.

[0209] Furthermore, in the second exposure step, in addition to the second resin composition layer, the first resin composition layer can also be exposed.

[0210] The second exposure step can be performed using the same method as the first exposure step. However, the terms "first pattern forming step" and "first resin composition" in the first exposure step are replaced with "second pattern forming step" and "second resin composition," respectively.

[0211] [Second Development Step]

[0212] The second pattern forming step, which includes a second developing step of developing the second resin composition layer with a developing solution to form a pattern, is preferred.

[0213] The second development step can be performed after the second preheating step described later. Furthermore, if the second pattern forming step includes the aforementioned second exposure step, it can be performed after the aforementioned second exposure step.

[0214] The second development step can be performed using the same method as the first development step. However, the terms "first pattern forming step" and "first resin composition" in the first development step are replaced with "second pattern forming step" and "second resin composition," respectively.

[0215] Furthermore, the development time in the second development step is preferably 1 to 20 minutes, and even better if it is 2 to 10 minutes.

[0216] The step of forming the second pattern is preferably a step of removing a portion of the second resin composition layer by solvent development. Solvent development refers to development using a developer containing an organic solvent as the developer.

[0217] The developer and rinsing solution used in the second development step can be the same as those used in the first development step, and the preferred sample is also the same.

[0218] <Second Preheating Step>

[0219] The method for manufacturing the permanent film of the present invention may include a step of heating the first pattern and the second resin composition layer (the second pre-heating step) after the step of forming the second resin composition layer and before the step of forming the second pattern.

[0220] By using the second preheating step, for example, the solubility of the second resin composition layer in the developer solution during the second development step can be adjusted, thereby making it easier to form a composite pattern.

[0221] The heating in the second preheating step can be performed, for example, by the same method as the first heating step described above.

[0222] The heating temperature and heating time in the second preheating step can be determined based on the components contained in the second resin composition and the developing solution used in the second developing step.

[0223] For example, a heating temperature of 80~180℃ is preferred, and 90~170℃ is even better.

[0224] <Second post-heating step>

[0225] The method for manufacturing the permanent film of the present invention preferably includes a heating step (second post-heating step) after the step of forming the second pattern described above.

[0226] In particular, at least one of the first resin composition and the second resin composition contains a polyimide precursor or a polyphenylene oxide precursor. In the case of azole precursors, during the second post-heating step, the polyimide precursor or polybenzo[a]pyrene precursor... Resins such as azole precursors are cyclized to form polyimides and polybenzo[a]pyrene. Resins such as azole.

[0227] Furthermore, cross-linking of unreacted polymeric groups in resins or compounds other than resins containing polymeric groups is also carried out.

[0228] The heating temperature (maximum heating temperature) in the second post-heating step is preferably 50~350℃, further preferably 150~250℃, even more preferably 160~250℃, and especially preferably 160~230℃.

[0229] The second post-heating step promotes the formation of the polyimide precursor or polystyrene in at least one of the first resin composition layer and the second resin composition layer by heating. The cyclization reaction of the azole precursor is preferred.

[0230] Regarding the heating in the second post-heating step, it is preferable to increase the temperature at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. A heating rate of 2 to 10°C / minute is more preferred, and 3 to 10°C / minute is even more preferred. By setting the heating rate to 1°C / minute or higher, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C / minute or lower, residual stress in the hardened material can be mitigated.

[0231] In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the initial 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.

[0232] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating process begins and reaches the maximum heating temperature. For example, the initial heating temperature is the temperature after developing the second resin composition layer, and it is preferable to start heating from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the first or second resin composition of this invention.

[0233] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0234] In particular, when forming a multilayered body, from the viewpoint of interlayer tightness, a heating temperature of 30°C or above is preferred, 80°C or above is even better, 100°C or above is further preferred, and 120°C or above is especially preferred.

[0235] The upper limit of the above heating temperature is preferably below 350°C, even better below 250°C, and further preferably below 240°C.

[0236] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, and then increasing the temperature from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment while irradiating with ultraviolet light. This pretreatment step can improve the properties of the layer. The pretreatment step can be performed in a short time, approximately 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferred. The pretreatment can be performed in two or more stages; for example, the first stage of pretreatment can be performed in the range of 100 to 150°C, followed by the second stage of pretreatment in the range of 150 to 200°C.

[0237] Furthermore, cooling can be performed after heating, and a cooling rate of 1~5℃ / minute is preferred at this time.

[0238] In terms of preventing the decomposition of specific resins, it is preferable to conduct the process in a low-oxygen environment by passing inert gases such as nitrogen, helium, or argon through the second post-heating step under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even better.

[0239] There are no particular limitations on the heating mechanism used in the second post-heating step; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0240] [Second post-exposure step]

[0241] Alternatively, a second post-heating step may be included in addition to the second post-heating step.

[0242] The second post-exposure step can be performed using the same method as the first post-development exposure step described above.

[0243] 〔filler〕

[0244] The second resin composition includes filler. Therefore, it is preferable that the second pattern includes filler.

[0245] The material and physical properties of the filler are the same as those used in the second resin composition described later.

[0246] The filler content in the second pattern is preferably 1% or more by volume relative to the volume of the second pattern, even better if it is 10% or more by volume, particularly good if it is 20% or more by volume, and best if it is 30% or more by volume.

[0247] Furthermore, a volume of 90% or less relative to the second pattern is preferred, 80% or less is even better, and 75% or less is optimal.

[0248] Furthermore, it is preferable that the filler content in the second pattern is 10% by mass or more relative to the total mass of the second pattern, and even more preferable that it is 30% by mass or more.

[0249] There is no particular upper limit to the above content, but 90% by mass or less is preferred, 80% by mass or less is even better, and 75% by mass or less is even more preferred.

[0250] <Metal Layer Formation Steps>

[0251] The composite pattern obtained by the second pattern forming step (preferably a pattern for the second post-heating step) can be used in the metal layer forming step of forming a metal layer on the composite pattern.

[0252] That is, the method for manufacturing the permanent film of the present invention preferably includes a metal layer forming step, which forms a metal layer on the obtained composite pattern (preferably the pattern for the second post-heating step).

[0253] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are preferred, with copper being even more preferred.

[0254] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), stripping, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited. As a preferred example of electroplating, electrolytic plating using copper sulfate or copper cyanide plating solutions can be cited.

[0255] For the thickness of the metal layer, a thickness of 0.01~50μm is preferred, and 1~10μm is even better.

[0256] Permanent film

[0257] The permanent film (i.e., composite pattern) obtained by the method of manufacturing the permanent film of the present invention contains polyimide or polyphenylene oxide. Azole is preferred.

[0258] Wherein, at least one of the first and second patterns forming the permanent film contains polyimide or polyphenylene oxide. Alzolium is acceptable, but both Pattern 1 and Pattern 2 contain polyimide or polybenzo[a]. The azole form is also one of the preferred forms of the present invention.

[0259] Among them, it is preferable that the permanent film obtained by the manufacturing method of the permanent film of the present invention contains polyimide.

[0260] At this point, it is sufficient that at least one of the first pattern and the second pattern forming the permanent film contains polyimide, but a state in which both the first pattern and the second pattern contain polyimide is also one of the preferred states of the present invention.

[0261] Polyimide, Polybenzox Cyclic resins such as azoles possess excellent heat resistance and insulation properties, thus enabling their inclusion in permanent films for various applications. While there are no particular limitations on these applications, examples of their use include as insulating or sealing materials or protective films in practical installation devices. Furthermore, they can also be used as base films or cover films for flexible substrates.

[0262] Furthermore, it is preferable that the elongation at break of the composite pattern obtained by the permanent film manufacturing method of the present invention is 40% or more, more preferably 50% or more, and even more preferably 60% or more.

[0263] [Pattern 1]

[0264] In the composite pattern (permanent film) of the present invention, the thickness of the first pattern is preferably 1~50μm, more preferably 2~20μm, and more preferably 3~15μm.

[0265] The coefficient of thermal expansion of the first pattern in the composite pattern of the present invention is preferably 2×10-6~50×10-5 / K, more preferably 1×10-5~30×10-5 / K, and even more preferably 2×10-5~20×10-5 / K.

[0266] In the composite pattern of the present invention, the relative permittivity of the first pattern under the following condition 1 (that is, the relative permittivity measured using the first resin composition under the following condition 1) is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably 3.3 or less. The lower limit of the above relative permittivity is not particularly limited, as long as it is 0 or more.

[0267] In the composite pattern of the present invention, it is preferable that the dielectric loss tangent of the first pattern is 0.1 or less under the following condition 1, more preferably 0.05 or less, and even more preferably 0.01 or less. The lower limit of the above dielectric loss tangent is not particularly limited, as long as it is 0 or more.

[0268] Regarding these physical properties, they can be measured by obtaining the first pattern from the composite pattern. Furthermore, in cases where obtaining the first pattern is more difficult, the first pattern can be formed on the substrate using the same steps as the first pattern forming steps used when forming the composite pattern.

[0269] [Pattern 2]

[0270] In the composite pattern (permanent film) of the present invention, the thickness of the second pattern is preferably 0.05~15μm, more preferably 0.1~5μm, and more preferably 0.2~2μm.

[0271] The coefficient of thermal expansion of the second pattern in the composite pattern of the present invention is preferably 0~30×10-5 / K, more preferably 1×10-6~20×10-5 / K, and even more preferably 1×10-5~10×10-5 / K.

[0272] Regarding these physical properties, they can be measured by obtaining a second pattern from the composite pattern. Furthermore, in cases where obtaining the second pattern is more difficult, the second pattern can be formed on the substrate using the same steps as those used in forming the composite pattern.

[0273] [The relationship between pattern 1 and pattern 2]

[0274] Regarding the ratio of the film thickness of the second pattern to the film thickness of the first pattern in the composite pattern of the present invention, the value represented by (film thickness of the second pattern) / (film thickness of the first pattern) is preferably 0.0001~1, more preferably 0.001~0.5, and even more preferably 0.01~0.1.

[0275] In the composite pattern of the present invention, it is preferred that the difference between the film thickness of the first pattern and the film thickness of the second pattern is 0~50μm, more preferably 0.01~20μm, and even more preferably 1~15μm.

[0276] Furthermore, the film thickness of both the first and second patterns can be large, but a smaller film thickness for the second pattern is preferable.

[0277] In the composite pattern of the present invention, it is preferable that the ratio of the coefficient of thermal expansion of the second pattern to that of the first pattern is 80% or less, more preferably 60% or less, further preferably 50% or less, and especially preferably 40% or less.

[0278] The above ratio is a value calculated using the following formula.

[0279] (Coefficient of thermal expansion of pattern 2) / (Coefficient of thermal expansion of pattern 1) × 100

[0280] There is no particular limitation on the lower limit of the above proportions, but it can also be 0% (below the detection limit).

[0281] In the composite pattern of the present invention, the difference between the coefficient of thermal expansion of the first pattern and the coefficient of thermal expansion of the second pattern is preferably 0~50×10-5 / K, more preferably 1×10-6~30×10-5 / K, and even more preferably 1×10-5~20×10-5 / K.

[0282] Furthermore, both the first and second patterns can have large coefficients of thermal expansion, but a larger coefficient of thermal expansion for the first pattern is preferable.

[0283] Regarding the ratio of the relative permittivity of the second pattern under the following condition 1 to the relative permittivity of the first pattern under the following condition 1, the value represented by (relative permittivity of the second pattern) / (relative permittivity of the first pattern) is preferably 0.1 to 1, more preferably 0.3 to 0.9, and even more preferably 0.5 to 0.8.

[0284] In the composite pattern of the present invention, the difference between the relative permittivity of the first pattern and the relative permittivity of the second pattern under the following condition 1 is preferably 0 to 3.0, more preferably 0.1 to 2.0, and even more preferably 0.2 to 1.0.

[0285] Furthermore, the relative permittivity of the first pattern under condition 1 and the relative permittivity of the second pattern under condition 1 can both be large, but a large relative permittivity of the first pattern is preferred.

[0286] Regarding the ratio of the dielectric loss tangent of the second pattern under the following condition 1 to the dielectric loss tangent of the first pattern under the following condition 1, the value represented by (dielectric loss tangent of the second pattern) / (dielectric loss tangent of the first pattern) is preferably 0.001 to 1, more preferably 0.005 to 0.5, and even more preferably 0.01 to 0.2.

[0287] In the composite pattern of the present invention, the difference between the dielectric loss tangent of the first pattern under the following condition 1 and the dielectric loss tangent of the second pattern under the following condition 1 is preferably 0 to 0.1, more preferably 0.0001 to 0.01, and even more preferably 0.001 to 0.005.

[0288] Furthermore, the dielectric loss tangent of the first pattern under condition 1 and the dielectric loss tangent of the second pattern under condition 1 can both be large, but it is better for the dielectric loss tangent of the second pattern to be small.

[0289] <Applications>

[0290] Examples of permanent films applicable to the manufacturing method of the permanent film of the present invention, or permanent films obtained by the manufacturing method of the permanent film of the present invention, include insulating films for devices, interlayer insulating films for redistribution layers, and stress-relief films. In addition, examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or patterns formed by etching insulating films used in practical installations as described above. For these applications, please refer to, for example, Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and Japan Polyimide / Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0291] Furthermore, the method for manufacturing the permanent film of the present invention, or the permanent film obtained by the method for manufacturing the permanent film of the present invention, can also be used in the manufacture of offset printing plates or screen printing plates, in the application of etching forming components, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0292] (Laminated bodies and methods for manufacturing laminated bodies)

[0293] In this invention, a laminate refers to a structure having a plurality of layers formed by a permanent film obtained by the method of manufacturing a permanent film according to this invention.

[0294] A laminate is a laminate consisting of two or more layers formed by a permanent film, and may also be a laminate consisting of three or more layers.

[0295] In the above-mentioned laminate, at least one of the two or more layers formed by the permanent film is a permanent film layer obtained by the permanent film manufacturing method of the present invention. From the viewpoint of suppressing the shrinkage of the permanent film or the deformation of the permanent film accompanying the shrinkage, it is also preferable that all the layers formed by the permanent film included in the above-mentioned laminate are permanent film layers obtained by the permanent film manufacturing method of the present invention.

[0296] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the permanent film of the present invention, and it is even more preferable to include repeating the steps of the method for manufacturing the permanent film of the present invention a plurality of times.

[0297] The laminate of the present invention comprises two or more layers formed of permanent films, and it is preferable that a metal layer is included between any one of the aforementioned permanent film layers. Regarding the aforementioned metal layer, it is preferable that it is formed by the aforementioned metal layer forming step.

[0298] That is, the method for manufacturing the laminate of the present invention, between a plurality of permanent film manufacturing methods, preferably includes a metal layer forming step of forming a metal layer on the layer formed by the permanent film. The preferred form of the metal layer forming step is as described above.

[0299] As an example of the aforementioned laminate, a laminate structure comprising at least three layers stacked sequentially: a first layer formed of a permanent film, a metal layer, and a second layer formed of a permanent film is preferred.

[0300] It is preferable that both the first and second permanent film layers described above are permanent film layers obtained by the permanent film manufacturing method of the present invention. The resin composition used to form the first and second permanent film layers may be of the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0301] <Layering Steps>

[0302] The method for manufacturing the laminate of the present invention preferably includes a lamination step.

[0303] The lamination process includes performing a series of steps, namely (a) the first pattern formation step, (b) the second layer formation step, and (c) the second pattern formation step, again on the surface of the composite pattern (permanent film) or metal layer. Depending on the requirements, the aforementioned second pre-heating step, second post-heating step, etc., may be further performed.

[0304] Furthermore, the metal layer formation step (d) can be included after (c) the second pattern forming step (preferably after the second post-heating step). It is self-evident that the aforementioned drying step, etc., can be further appropriately included in the lamination step.

[0305] If a further deposition step is performed after the deposition step, a surface activation treatment step may be performed after the first pattern formation step (a) described above, after the second pattern formation step (c) described above (or, after the second post-heating step) described above, or after the metal layer formation step (d) described above. Plasma treatment can be exemplified as a surface activation treatment. Details of the surface activation treatment will be described later.

[0306] It is preferable to perform the above-mentioned layering steps 2 to 20 times, and even better to perform them 2 to 9 times.

[0307] For example, in a structure of resin layer (permanent film) / metal layer / resin layer (permanent film) / metal layer / resin layer (permanent film) / metal layer, it is preferable to have a resin layer (permanent film) of 2 or more layers and less than 20 layers, and it is even more preferable to have a structure of 2 or more layers and less than 9 layers.

[0308] The composition, shape, and thickness of each of the above layers can be the same or different.

[0309] In this invention, it is particularly preferred that the permanent film be formed by further covering the metal layer after the metal layer is formed using the above-described method for manufacturing a permanent film. Specifically, an example is that the following steps are repeated sequentially: (a) the first pattern forming step, (b) the second layer forming step, (c) the second pattern forming step, and (d) the metal layer forming step. By alternately performing the deposition steps of the permanent film and the metal layer forming step obtained by the method for manufacturing a permanent film of this invention, the permanent film and the metal layer obtained by the method for manufacturing a permanent film of this invention can be deposited alternately.

[0310] (Surface activation treatment step)

[0311] The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the metal layer and the permanent film.

[0312] The surface activation treatment step is usually performed after the metal layer formation step, but it can also be performed after the second pattern formation step in (c) above (preferably after the second post-heating step), after the surface activation treatment step of the permanent film, and then the metal layer formation step.

[0313] Regarding the surface activation treatment, it can be performed on at least a portion of the metal layer, on at least a portion of the permanent film, or on at least a portion of both the metal layer and the permanent film. It is preferable to perform surface activation treatment on at least a portion of the metal layer, and it is preferable to perform surface activation treatment on a portion or all of the region of the metal layer where the permanent film is formed on the surface. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the permanent film disposed on its surface can be improved.

[0314] Furthermore, it is preferable to perform surface activation treatment on part or all of the permanent film. In this way, by performing surface activation treatment on the surface of the permanent film, the adhesion between the permanent film and the metal layer disposed on the surface-activated surface can be improved. In particular, in cases where the permanent film is hardened, such as during negative development, it is less likely to be damaged by the surface treatment, thereby easily improving the adhesion.

[0315] As a surface activation treatment, specifically, plasma treatment, corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, and NF3 / O2, surface treatment based on ultraviolet (UV) ozone method, immersion treatment in hydrochloric acid aqueous solution to remove oxide film followed by immersion in an organic surface treatment agent containing at least one amine group and a thiol group, and mechanical roughening treatment using a brush are preferred, especially oxygen plasma treatment using oxygen as the raw gas. In the case of corona discharge treatment, an energy of 500~200,000 J / m2 is preferred, 1000~100,000 J / m2 is more preferred, and 10,000~50,000 J / m2 is optimal.

[0316] (Manufacturing method of the device)

[0317] The present invention also discloses a method for manufacturing an apparatus including the method for manufacturing a permanent film of the present invention or the method for manufacturing a laminate of the present invention.

[0318] Examples of devices include semiconductor devices and electronic devices.

[0319] As a specific example of an apparatus for using the permanent film obtained by the method of manufacturing the permanent film of the present invention in the formation of an interlayer insulating film for a rewiring layer, one can refer to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in Figure 1, and such contents are incorporated into this specification.

[0320] (First resin composition and second resin composition)

[0321] The components contained in the resin composition of the present invention will be described in detail below.

[0322] The first resin composition and the second resin composition can be the same composition or they can be different compositions.

[0323] In particular, while the second resin composition contains fillers, it is also preferable to use a composition that does not contain fillers or a composition in which the filler content in the first resin composition is lower than that in the second resin composition. Based on this approach, as described above, it is possible to achieve both the improved adhesion based on the second pattern and the mitigation of mechanical stress based on the first pattern.

[0324] Specifically, the filler content relative to the total solids content of the first resin composition can be set, for example, to 5% by mass or less. A content of 3% by mass or less is preferred, and 1% by mass or less is even more preferred. The lower limit of the above content is not particularly limited and can be 0% by mass.

[0325] Furthermore, for example, the ratio expressed as (the content of filler relative to the total solids content of the first resin composition) / (the content of filler relative to the total solids content of the second resin composition) can be set to 0.10 or less. A ratio of 0.06 or less is preferred, and 0.02 or less is even more preferred. There is no particular limitation on the lower limit of the above ratio, but it can also be 0.

[0326] From the viewpoint of the close contact between the first pattern and the second pattern, filler can also be included in the first resin composition.

[0327] The first resin composition is preferably a negative photosensitive resin composition.

[0328] Negative photosensitive resin composition is the composition used in the formation of negative photosensitive layer.

[0329] The first resin composition preferably comprises a composition containing at least one of a resin and a photopolymerization initiator and a photoacid generator; more preferably, it comprises a composition containing a resin and a photopolymerization initiator; and even more preferably, it comprises a resin, a photopolymerization initiator, and a polymerizable compound.

[0330] Furthermore, the resin contained in the first resin composition is a polyimide precursor or a polyphenylene oxide precursor. Azole precursors are preferred.

[0331] These components will be discussed later.

[0332] The second resin composition is preferably a thermosetting resin composition.

[0333] Furthermore, it is preferable that the second resin composition contains a thermal polymerization initiator.

[0334] The second resin composition preferably contains a resin having a polymerizable group. Preferably, the polymerizable group is a group capable of forming a polymer with the resin or polymeric compound contained in the first resin composition. For example, if the first resin composition contains a free radical polymerizable compound, it is preferable that the second resin composition contains a resin having a free radical polymerizable group.

[0335] Furthermore, the resin contained in the second resin composition is a polyimide precursor or a polyphenylene oxide. Azole precursors are preferred.

[0336] Furthermore, considering the close contact between the first and second patterns in the composite pattern, it is preferable that the resin contained in the first resin composition and the resin contained in the second resin composition are the same type of resin. For example, it is preferable that both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors. It is believed that when both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors, the elongation at break of the obtained permanent film is also improved.

[0337] Furthermore, it is preferable that the second resin composition contains a polymerizable compound having an aromatic group. According to this approach, the relative permittivity of the second pattern decreases, thereby sometimes achieving suppression of increased wiring resistance, suppression of decreased resistance of the permanent film, and reduction of propagation delay.

[0338] These components will be discussed later.

[0339] The second resin composition preferably has a relative permittivity of 4.0 or less under condition 1 below, more preferably 3.5 or less, and even more preferably 3.0 or less. There is no particular limitation on the lower limit of the aforementioned relative permittivity; it is acceptable as long as it is 0 or more.

[0340] The dielectric loss tangent of the second resin composition is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less under the following condition 1. There is no particular limitation on the lower limit of the dielectric loss tangent; it is acceptable as long as it is 0 or more.

[0341] Condition 1: The composition is coated with a thickness of 15 μm onto a silicon wafer with an oxide film (SiO2) formed on its surface, dried at 100°C for 5 minutes, and heated at 230°C for 180 minutes to prepare a hardened film. The relative permittivity and dielectric loss tangent of the individual film of the composition prepared by immersing it in hydrogen fluoride are measured.

[0342] The relative permittivity and dielectric loss tangent can be measured according to JIS (Japanese Industrial Standards) R 1641 "Method for determination of microwave dielectric properties of precision ceramic substrates".

[0343] The components contained in the first resin composition and the second resin composition are described in detail below.

[0344] In the following description, when simply referred to as "resin composition", it refers to both the first resin composition and the second resin composition.

[0345] Furthermore, in the following description, unless otherwise specifically stated that fillers are included, the description of "total solids content" is assumed to be replaced by "total solids content excluding fillers" in the second resin composition. Similarly, if the first resin composition contains fillers, it is also assumed to be replaced by "total solids content excluding fillers".

[0346] <packing>

[0347] The second resin composition of the present invention includes filler.

[0348] The first resin composition of the present invention may contain fillers.

[0349] The packing material can be either organic or inorganic.

[0350] The filler included in the second resin composition is preferably selected from at least one filler selected from the group consisting of silicon dioxide, quartz, glass, ceramics, fluoropolymers and liquid crystal polymers.

[0351] Examples of silica include molten silica, precipitated silica, fumigated silica, colloidal silica, and synthetic silica.

[0352] Examples of ceramic materials include alumina, zirconium dioxide, barium titanate, hydroxyapatite, silicon nitride, silicon carbide, fluorite, magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, saponite, and pyrophyllite.

[0353] Examples of fluoropolymers include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluoropolymers, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer.

[0354] Examples of liquid crystal polymers include aromatic polyesters.

[0355] Furthermore, these materials can be used in combination. For example, materials composed of silicon dioxide-coated fluororesin particles can also be used.

[0356] There are no particular limitations on the shape of the filler, but fibrous, plate-like, scaly, rod-like, spherical, tubular, curved plate-like, needle-like, etc., can be used without particular restrictions.

[0357] From the viewpoint of reducing dielectric constant, it is preferable that the filler be selected from at least one type of filler including hollow particles and porous particles.

[0358] When the filler is a hollow particle or a porous particle, a porosity of 15-99.5% is preferred, 30-98% is even better, and 40-92% is further preferred.

[0359] From the perspective of suppressing the increase of wiring resistance and suppressing the decrease of permanent film resistance, the relative permittivity of the filler is preferably below 10, 1.0~5.0 is even better, and 2.0~4.0 is even better.

[0360] From the perspective of suppressing the increase in wiring resistance and the decrease in the resistance of permanent film, a dielectric loss tangent of 0.01 or less is preferred, 0.005 or less is even better, and 0.002 or less is further preferred. The lower limit of the dielectric loss tangent is not particularly limited, but it can also be 0.

[0361] The relative permittivity and dielectric loss tangent mentioned above were calculated for the compounds themselves using JIS (Japanese Industrial Standards) C 2138:2007.

[0362] The particle size of the filler is preferably below 1 μm, even better below 0.5 μm, and further preferably below 0.2 μm.

[0363] Furthermore, it is preferable for the filler to have a volume average particle size of 0.002 μm or more, even better for 0.01 μm or more, and even more preferably for 0.02 μm or more.

[0364] The aforementioned particle size was calculated using the method described in the examples described later.

[0365] The packing material can be a granular mixture comprising at least two groups of particles with different particle sizes. The "particle size" of a particular particle group is determined using the same method as for the "particle size" of the packing material. With this structure, smaller particles are embedded between larger particles, reducing the spacing between the packing materials compared to a packing material containing only a single diameter, thus increasing the contact points and improving thermal conductivity. For example, in the case of a mixture of two groups of particles with different particle sizes, two peaks are observed in the particle size distribution of the packing material containing these particle groups. Therefore, by identifying the number of peaks in the particle size distribution of the packing material, it is possible to confirm that the granular mixture used as the packing material contains several groups of particles with different particle sizes.

[0366] When there are multiple peaks in the particle size distribution of the packing material, a peak-to-particle size ratio (equivalent to the ratio of the particle sizes at the peak apex to each other) of 1.5 to 50 is preferred between at least two peaks. A lower limit of 2 or higher is preferred, and 4 or higher is even better. An upper limit of 40 or lower is preferred, and 20 or lower is even better. As long as the peak-to-particle ratio is within the above range, large-diameter packing material is prevented from becoming coarse particles, while small-diameter packing material tends to occupy the space between large-diameter packing material.

[0367] Furthermore, among at least two peak values, a peak intensity ratio of 0.2 to 5.0 between the larger and smaller peak values ​​is preferred. A lower limit of 0.2 or higher is preferred, and 0.5 or higher is even better. An upper limit of 5.0 or lower is preferred, and 3.0 or lower is even better.

[0368] The filler can be electrically insulating, semiconductor, or conductive, but from the perspective of the insulation of the permanent film, electrical insulation is preferred. The degree of electrical insulation and conductivity should be appropriately selected according to the design or purpose.

[0369] The lower limit of the volume resistivity of the filler is preferably 1.0 × 10¹¹ Ω·cm or higher, more preferably 3.0 × 10¹¹ Ω·cm or higher, and especially preferably 1.0 × 10¹² Ω·cm or higher. There is no particular limit to the upper limit of the volume resistivity, but for example, 1.0 × 10¹⁹ Ω·cm or lower is preferred.

[0370] On the other hand, in the case of semiconductor or conductive fillers, there is no particular limitation on the lower limit of the volume resistivity of the filler, but it is preferred to be 1.0 × 10⁻⁷ Ω·cm or higher. Furthermore, it is preferred that the upper limit of the volume resistivity does not reach 1.0 × 10¹¹ Ω·cm.

[0371] From the viewpoint of sedimentation within the composition, a density of the filler is preferably 20.0 g / cm³ or less, more preferably 10.0 g / cm³ or less, and even more preferably 5.0 g / cm³ or less. Furthermore, there is no particular limitation on the lower limit of the filler density, but for example, 0.5 g / cm³ or more is preferred. Moreover, when the filler is porous or consists of hollow particles or other materials with voids or cavities, the density of the filler in this specification refers to the density of the solid components constituting the filler.

[0372] The thermal expansion coefficient of the packing material is preferably below 10×10⁻⁵ / K, and even more preferably below 3×10⁻⁵ / K. Furthermore, there is no particular lower limit to the thermal expansion coefficient of the packing material, but for example, above 0 / K is preferred.

[0373] Considering the excellent adhesion to metal even after a long period of time, it is preferable that the filler content relative to the total solids content of the second resin composition, including the filler, is 0.2% by mass or more, more preferably 2.0% by mass or more, and even more preferably 10% by mass or more. There is no particular upper limit to the above content, but 80% by mass or less is preferable, 70% by mass or less is more preferable, and 55% by mass or less is even more preferable.

[0374] It is preferable that the filler content relative to the total solids content of the first resin composition, including the filler, is 0% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5% by mass or more. There is no particular upper limit to the above content, but it is preferable that it is 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0375] As described above, the content of the filler relative to the total solids content of the filler in the first resin composition can also be set to be less than the content of the filler relative to the total solids content of the filler in the second resin composition.

[0376] As described above, one type of packing material or two or more types of packing materials can be used. When two or more types of packing materials are used, the total amount of such packing materials is preferably within the range described above.

[0377] <Resin>

[0378] The resin composition of the present invention comprises resin.

[0379] Examples of resins include cyclized resins and their precursors (specific resins) as shown below, as well as other resins.

[0380] <Specific Resin>

[0381] It is preferable that the resin composition of the present invention comprises at least one resin (specific resin) selected from the group including cyclized resins and their precursors.

[0382] Cyclic resins contain amide ring structures or amide ring structures in their main chain structure. Resins with an azole ring structure are preferred.

[0383] In this invention, the main chain refers to the longest bond chain in the resin molecule.

[0384] Examples of cyclized resins include polyimide and polybenzo[a]pyridine. Zyrazole, polyamide, etc.

[0385] Precursors to cyclized resins refer to resins that undergo chemical structural changes due to external stimuli to become cyclized resins. Resins that undergo chemical structural changes due to heat to become cyclized resins are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become cyclized resins are even better.

[0386] Examples of precursors for cyclized resins include polyimide precursors and polyphenylene oxide precursors. Azole precursors, polyamide-imide precursors, etc.

[0387] That is, the resin composition of the present invention comprises a material selected from polyimide, polyimide precursor, polyphenylene oxide, etc. azole, polybenzo[a] It is preferred that at least one resin (specific resin) from the group consisting of azole precursors, polyamide imides and polyamide imides is used as the specific resin.

[0388] It is preferable that the resin composition of the present invention contains polyimide or polyimide precursor as a specific resin.

[0389] Furthermore, it is preferable for a particular resin to have polymerizable groups, and even more preferable if it contains free radical polymerizable groups.

[0390] When a particular resin has free radical polymerizable groups, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later, and it is even more preferable that it includes both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Furthermore, depending on the need, it can include the sensitizer described later. Such a resin composition of the present invention can, for example, form a negative photosensitive layer.

[0391] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups.

[0392] In cases where a particular resin has acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid-generating agent described later. Such a resin composition of the present invention can be used to form, for example, a chemically amplified positive or negative photosensitive layer.

[0393] [Polyimide precursor]

[0394] The type of polyimide precursor used in this invention is not particularly specified, but it is preferred to include repeating units represented by the following formula (2).

[0395] [Chemical Formula 1]

[0396] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 independently represent hydrogen atoms or monovalent organic groups.

[0397] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, with oxygen atoms being preferred.

[0398] In formula (2), R111 represents a divalent organic group. Examples of divalent organic groups include aliphatic groups, cyclic aliphatic groups, and aromatic groups comprising straight or branched chains, preferably aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof, and more preferably an aromatic group comprising 6 to 20 carbon atoms. The aforementioned straight or branched aliphatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the chain, and the aforementioned cyclic aliphatic groups and aromatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the ring member. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, particularly those represented by -Ar-L-Ar-. Wherein, Ar is an aromatic group independently, and L is a group comprising a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

[0399] R111 is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more may be used.

[0400] Specifically, diamines comprising aliphatic groups having 2 to 20 carbon atoms (linear or branched), cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms, or combinations thereof, are preferred; diamines comprising aromatic groups having 6 to 20 carbon atoms are even more preferred. The aforementioned linear or branched aliphatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the chain, and the aforementioned cyclic aliphatic and aromatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the ring. Examples of groups comprising aromatic groups are as follows.

[0401]

[0402] In the formula, A represents a single bond or a divalent linker, preferably selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof. It is more preferred to select groups selected from alkyl groups with 1 to 3 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-. -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2- are even more preferred.

[0403] In the formula, * indicates the bonding location with other structures.

[0404] As a diamine, specifically, examples include 1,2-diaminoethane, 1,2- Diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diamino Diphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4,4'-diaminodibenzophenone or 3,3'-diaminodibenzophenone, 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(4-aminophenyl)hexafluoropropane, (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) arsenide, bis(4-amino-3-hydroxyphenyl) arsenide, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] arsenide, bis[4-(3-aminophenoxy)phenyl] arsenide, bis[4-(2-aminophenoxy)phenyl] arsenide, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl arsenide, 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)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonate, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-Diaminophen, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, 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)tetrafluoroheptane, 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, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl At least one diamine selected from the following: 3,4'-amino-2-trifluoromethylphenoxy)diphenyl benzoyl, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl benzoyl, 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'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0405] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0406] Alternatively, it can be preferably used as a diamine having two or more alkyl diol units as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 on the main chain.

[0407] From the viewpoint of the flexibility of the obtained organic membrane, R111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a group including an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. It is preferable that Ar is phenyl, and it is preferable that L is an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, it is preferable that the aliphatic hydrocarbon group is alkyl.

[0408] Furthermore, from the viewpoint of i-ray transmittance, it is preferable that R111 is a divalent organogroup represented by formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organogroup represented by formula (61) is more preferable.

[0409]

[0410] In formula (51), R50 to R57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R50 to R57 is a fluorine atom, a methyl group or a trifluoromethyl group. * represents the bonding site with the nitrogen atom in formula (2).

[0411] Examples of monovalent organic groups in R50 to R57 include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0412]

[0413] In formula (61), R58 and R59 are fluorine atoms, methyl or trifluoromethyl atoms, respectively, and * represents the bonding sites with nitrogen atoms in formula (2).

[0414] Examples of diamines providing 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. One or more of these may be used in combination.

[0415] Furthermore, it is preferable that R111 contains a polycyclic aromatic ring structure. In particular, it is preferable that R111 contains a polycyclic aromatic ring structure when the second resin composition contains a resin having a repeating unit represented by formula (2).

[0416] Based on this state, the relative permittivity of the permanent film can be reduced, thereby sometimes achieving the suppression of increased wiring resistance and the suppression of decreased permanent film resistance.

[0417] Examples of polycyclic aromatic ring structures include biphenyl structures, triphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fumonisin ring structures, acenaphthene ring structures, etc., but are not limited to these.

[0418] Of these, R111 preferably contains at least one of a polybenzene structure or a cyclohexane structure.

[0419] In formula (2), R115 represents a tetravalent organogroup. As a tetravalent organogroup, a tetravalent organogroup containing an aromatic ring is preferred, and the group represented by formula (5) or formula (6) below is even more preferred.

[0420] In equation (5) or equation (6), * independently represents the bonding location with other structures.

[0421]

[0422] In formula (5), R112 is a single bond or a divalent linker, preferably selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO- and groups in combination thereof, preferably selected from single bonds, alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably selected from divalent groups including -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0423] Furthermore, R115 containing a multi-ring aromatic ring structure is also preferable. Based on this state, the relative permittivity of the permanent film can be reduced, thereby sometimes achieving the suppression of increased wiring resistance and the suppression of decreased permanent film resistance.

[0424] Examples of polycyclic aromatic ring structures include biphenyl structures, triphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fumonisin ring structures, acenaphthene ring structures, etc., but are not limited to these.

[0425] Of these, R115 preferably contains at least one of a polybenzene structure or a cyclohexane structure.

[0426] Specifically, R115 can be exemplified by the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride. As the structure corresponding to R115, the polyimide precursor may contain only one type of tetracarboxylic acid dianhydride residue, or it may contain two or more types.

[0427] Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0428]

[0429] In formula (O), R115 represents a tetravalent organic group. The preferred range of R115 is the same as that of R115 in formula (2), and the preferred range is also the same.

[0430] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide 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'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Alkane dianhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrides, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydrides, 1,4,5,6-naphthalenetetracarboxylic acid dianhydrides, 2,2',3,3'-diphenyltetracarboxylic acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,2,4,5-naphthalenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and such alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0431] Alternatively, the tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as a better example.

[0432] In formula (2), at least one of R111 and R115 can also have an OH group. More specifically, as R111, residues of diaminophenol derivatives can be cited.

[0433] In formula (2), R113 and R114 independently represent a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group comprises a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R113 and R114 contains a polymerizable group, and even more preferable that both contain polymerizable groups. It is also preferable that at least one of R113 and R114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing cross-linking reactions by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acetoxymethyl groups, epoxy groups, oxybutyl groups, and benzo[a] groups. Azolium group, block isocyanate group, amine group. For polyimide precursors, groups with vinyl unsaturated bonds are preferred due to their free radical polymerization properties.

[0434] Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with the group represented by formula (III) below being preferred.

[0435]

[0436] In formula (III), R200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

[0437] In equation (III), * indicates the bonding site with other structures.

[0438] In formula (III), R201 represents a alkyl group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, cycloalkyl group or polyalkylene group.

[0439] Examples of preferred R201 include alkylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, polyalkylene, alkylene, propylene, -CH2CH(OH)CH2-, cyclohexylene, polyalkylene, and alkylene, with alkylene, propylene, or polyalkylene being even more preferred.

[0440] In this invention, polyalkylene oxide refers to an alkylene oxide group directly bonded to two or more groups. The alkylene groups in the plurality of alkylene oxide groups contained in the polyalkylene oxide group may be the same or different.

[0441] When a polyalkoxy group contains multiple alkoxy groups with different alkyl groups, the arrangement of the alkoxy groups in the polyalkoxy group can be random, block-shaped, or alternating.

[0442] It is preferred that the carbon number of the above-mentioned alkyl group (in the case that the alkyl group has substituents, the carbon number including the substituents) is 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is the best.

[0443] Furthermore, the aforementioned alkyl groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0444] Furthermore, the number of polyalkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0445] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propoxy groups are preferred as polyvinyloxy groups. Polyvinyloxy or polypropyleneoxy is more preferred, and polyvinyloxy is even more preferred. Among the groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propoxy groups, the ethyleneoxy and propoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred states of repeating ethyleneoxy groups are as described above.

[0446] In formula (2), when R113 is a hydrogen atom or when R114 is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylene unsaturated bond. An example of such a tertiary amine compound having an ethylene unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0447] In formula (2), at least one of R113 and R114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it is a base-soluble group such as a phenolic hydroxyl group or a carboxyl group that decomposes under the action of acid. However, acetal, ketal, silyl alkyl, silyl ether, and tertiary alkyl ester groups are preferred. From the point of view of exposure sensitivity, acetal or ketal is more preferred.

[0448] Specific examples of acid-degrading groups include tributoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tributoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0449] Furthermore, it is preferable that the polyimide precursor contains fluorine atoms in its structure. A fluorine atom content of 10% by mass or more, and less than 20% by mass, is preferred in the polyimide precursor.

[0450] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0451] It is preferable that the repeating unit represented by formula (2) is the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in this invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased.

[0452] Equation (2-A)

[0453] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group, preferably both of which are groups containing polymerizable groups.

[0454] A1, A2, R111, R113 and R114 are independently the same as A1, A2, R111, R113 and R114 in equation (2), and the preferred range is also the same.

[0455] R112 has the same meaning as R112 in equation (5), and the preferred range is also the same.

[0456] Polyimide precursors may contain one repeating unit represented by formula (2), or two or more repeating units. They may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it is self-evident that polyimide precursors may contain other types of repeating units besides the repeating unit of formula (2).

[0457] As one embodiment of the polyimide precursor in this invention, an example is provided where the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is especially preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyimide precursor, except for the terminal units, can also be the repeating units represented by formula (2).

[0458] 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) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0459] It is preferred that the molecular weight dispersion of the above-mentioned polyimide precursor is 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, for example, it is preferred to be 7.0 or lower, more preferably 6.5 or lower, and further preferably 6.0 or lower.

[0460] In this specification, the molecular weight dispersion is a value calculated using the weight average molecular weight / number average molecular weight.

[0461] Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are within the aforementioned ranges.

[0462] [Polyimide]

[0463] The polyimide used in this invention can be an alkali-soluble polyimide or a polyimide soluble in a developer solution with organic solvents as the main component.

[0464] In this specification, alkali-soluble polyimide refers to polyimide that dissolves at least 0.1 g in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From a pattern-forming point of view, dissolving at least 0.5 g of polyimide is preferred, and dissolving at least 1.0 g of polyimide is further preferred. There is no particular upper limit to the above-mentioned dissolution amount, but less than 100 g is preferred.

[0465] Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyimide with multiple polyimide structures in the main chain is preferred.

[0466] In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to any other bonded chain.

[0467] -Fluorine atom-

[0468] From the perspective of the strength of the obtained organic membrane, polyimide with fluorine atoms is also preferable.

[0469] It is preferable that the fluorine atom is included, for example, in R132 or R131 of the repeating unit represented by the following formula (4), and even more preferably, it is included as a fluorinated alkyl group in R132 or R131 of the repeating unit represented by the following formula (4).

[0470] The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more, and preferably less than 20% by mass.

[0471] -Silicon Atom-

[0472] From the perspective of the strength of the obtained organic membrane, polyimide with silicon atoms is also preferable.

[0473] It is preferable that the silicon atom is included in R131 of the repeating unit represented by the following formula (4), and even more preferable that it is included in R131 of the repeating unit represented by the following formula (4) as an organic modified (poly)siloxane structure.

[0474] Furthermore, the aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structures can also be included on the side chains of polyimide, but it is preferable that they are included on the main chain of polyimide.

[0475] The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and less than 20% by mass is even better.

[0476] -Ethylene unsaturated bond-

[0477] From the perspective of the strength of the obtained organic membrane, polyimide with vinyl unsaturated bonds is preferred.

[0478] Polyimide can have ethylene unsaturated bonds at the end of the main chain or on the side chain, but it is better to have ethylene unsaturated bonds on the side chain.

[0479] The aforementioned ethylene-type unsaturated bonds exhibit better free radical polymerization properties.

[0480] It is preferable that the ethylene unsaturated bond is contained in R132 or R131 of the repeating unit represented by the following formula (4), and it is even more preferable that it is contained in R132 or R131 of the repeating unit represented by the following formula (4) as a group having an ethylene unsaturated bond.

[0481] In these cases, it is preferable that the ethylene unsaturated bond is contained in R131 of the repeating unit represented by the following formula (4), and it is even more preferable that it is contained in R131 of the repeating unit represented by the following formula (4) as a group having an ethylene unsaturated bond.

[0482] Examples of groups having vinyl unsaturated bonds include vinyl, allyl, vinylphenyl, and other vinyl groups that are directly bonded to an aromatic ring and can be substituted, as well as (meth)acrylyl, (meth)acryloxy, and groups represented by formula (IV) below.

[0483]

[0484] In formula (IV), R20 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

[0485] In formula (IV), R21 represents an alkyl group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyl group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and especially preferably 2 or 3 carbon atoms; preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and especially preferably 1 to 3 carbon atoms), or a group formed by combining two or more of these.

[0486] Furthermore, the alkyl group having 2 to 12 carbon atoms can be any one of linear, branched, cyclic, or alkyl groups represented by such combinations.

[0487] As for the above-mentioned alkyl groups having 2 to 12 carbon atoms, alkyl groups having 2 to 8 carbon atoms are preferred, and alkyl groups having 2 to 4 carbon atoms are even more preferred.

[0488] In these cases, it is preferable that R21 is a group represented by any one of the following formulas (R1) to (R3), with the group represented by formula (R1) being more preferred.

[0489]

[0490] In formulas (R1) to (R3), L represents a single bond or an alkyl group having 2 to 12 carbon atoms, a (poly)alkyl group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a bonding site with the oxygen atom bonded to R21 in formula (IV).

[0491] In formulas (R1) to (R3), the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly) alkoxy group having 2 to 30 carbon atoms in L is the same as the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly) alkoxy group having 2 to 30 carbon atoms in R21 above.

[0492] In formula (R1), it is preferable that X is an oxygen atom.

[0493] In equations (R1) to (R3), * has the same meaning as * in equation (IV), and the better state is also the same.

[0494] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups or other hydroxyl groups with a compound having isocyanate groups and vinyl unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0495] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an vinyl unsaturated bond (e.g., 2-hydroxyethyl methacrylate).

[0496] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups with a compound having glycidyl methacrylate and vinyl unsaturated bonds (e.g., glycidyl methacrylate).

[0497] In formula (IV), * indicates the bonding site with other structures, and the bonding site with the main chain of polyimide is preferred.

[0498] The amount of vinyl unsaturated bonds relative to the total mass of polyimide is preferably 0.0001~0.1 mol / g, and even more preferably 0.0005~0.05 mol / g.

[0499] - Polymerizable groups other than those with ethylene unsaturated bonds-

[0500] Polyimide can have polymerizable groups other than those with ethylene unsaturated bonds.

[0501] Examples of polymerizable groups other than those with vinyl unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups.

[0502] It is preferable that polymeric groups other than those with ethylene unsaturated bonds are included, for example, in R131 of the repeating unit represented by formula (4) described later.

[0503] The amount of polymerizable groups other than those with ethylene unsaturated bonds relative to the total mass of polyimide is preferably 0.0001~0.1 mol / g, and more preferably 0.001~0.05 mol / g.

[0504] -Polar conversion group-

[0505] Polyimide can have polar conversion groups such as acid-degradable groups. The acid-degradable groups in polyimide are the same as those described in R113 and R114 in the above formula (2), and the preferred state is also the same.

[0506] Polar conversion groups are included, for example, in R131, R132, the end of polyimide, etc., of the repeating unit represented by formula (4) described later.

[0507] -Acid Value-

[0508] When polyimide is used for alkaline development, from the viewpoint of improving developability, it is preferable for the acid value of polyimide to be 30 mg KOH / g or higher, even better for 50 mg KOH / g or higher, and further preferred for 70 mg KOH / g or higher.

[0509] Furthermore, an acid value of 500 mg KOH / g or less is preferred, 400 mg KOH / g or less is even better, and 200 mg KOH / g or less is even more preferred.

[0510] Furthermore, when polyimide is used in development with a developer solution mainly composed of organic solvents (e.g., "solvent development" as described below), the acid value of polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0511] The acid value mentioned above is determined by known methods, such as the method described in JIS K 0070:1992.

[0512] Furthermore, considering both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred among the acid groups contained in polyimide, while those with a pKa of 3 to 8 are even better.

[0513] pKa is the negative common logarithm of the equilibrium constant Ka, which takes into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD / ChemSketch (registered trademark). See also the values ​​disclosed in the "Revised 5th Edition of the Chemical Handbook: Basic Edition" edited by the Chemical Society of Japan.

[0514] Alternatively, in the case where the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0515] As such an acid group, polyimide preferably contains at least one group selected from the group including carboxyl groups and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0516] -Phenolic hydroxyl-

[0517] From the viewpoint of making the development speed of alkaline developer suitable, polyimide with phenolic hydroxyl groups is preferred.

[0518] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0519] It is preferable that the phenolic hydroxyl group is contained in R132 or R131 of the repeating unit represented by formula (4) described below.

[0520] The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1~30 mol / g, and even better is 1~20 mol / g.

[0521] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferred to include repeating units represented by the following formula (4).

[0522]

[0523] In equation (4), R131 represents a divalent organic group and R132 represents a tetravalent organic group.

[0524] In the case of having a polymerizable group, the polymerizable group may be located on at least one of R131 and R132, as shown in formula (4-1) or formula (4-2) below, or it may be located at the end of the polyimide.

[0525]

[0526] In formula (4-1), R133 is a polymerizable group, and the other groups have the same meaning as in formula (4).

[0527]

[0528] At least one of R134 and R135 is a polymeric group, and if it is not a polymeric group, it is an organic group. The other groups have the same meaning as in formula (4).

[0529] Examples of polymerizable groups include groups containing ethylene unsaturated bonds or crosslinking groups other than those containing ethylene unsaturated bonds.

[0530] R131 represents a divalent organogroup. As a divalent organogroup, it can be exemplified by the same type as R111 in formula (2), and the preferred range is also the same.

[0531] Furthermore, R131 can be a diamine residue remaining after the amino group of the diamine is removed. As a diamine, aliphatic, cyclic aliphatic, or aromatic diamines can be cited. As a specific example, R111 in formula (2) of polyimide precursors can be cited.

[0532] From the viewpoint of more effectively suppressing warping during calcination, R131 is preferably a diamine residue having at least two alkyl diol units on the main chain. More preferably, it contains a total of two or more diamine residues of either or both of ethylene glycol chains and propylene glycol chains in a molecule, and even more preferably, it is the above-mentioned diamine without containing diamine residues of an aromatic ring.

[0533] Examples of diamines containing a total of two or more ethylene glycol chains or propylene glycol chains in one molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (these are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but are not limited to these.

[0534] R132 represents a tetravalent organogroup. As a tetravalent organogroup, it can be exemplified by the same type as R115 in formula (2), and the preferred range is also the same.

[0535] For example, the four bonded groups of the tetravalent organic group exemplified as R115 bond with the four -C(=O)- portions in the above formula (4) to form a condensation ring.

[0536] Furthermore, R132 can be a tetracarboxylic acid residue remaining after the anhydride group is removed from a tetracarboxylic acid dianhydride. As a specific example, R115 in formula (2) of a polyimide precursor can be cited. From the viewpoint of the strength of the organic film, R132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0537] It is also preferable that at least one of R131 and R132 has an OH group. More specifically, as R131, 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-mentioned (DA-1) to (DA-18) are preferred examples, and as R132, the above-mentioned (DAA-1) to (DAA-5) are more preferred examples.

[0538] Furthermore, it is preferable that polyimide contains fluorine atoms in its structure. A fluorine atom content of 10% by mass or more, and less than 20% by mass, is preferred in polyimide.

[0539] Furthermore, to improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0540] Furthermore, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorinated compounds, and monoactive ester compounds. Among these, monoamines are preferred, and preferred compounds for monoamines 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-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-7-aminonaphthalene. Examples of aminobenzene compounds include 2-carboxy-7-aminobenzene, 2-carboxy-6-aminobenzene, 2-carboxy-5-aminobenzene, 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-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. Two or more of these compounds can be used, and by reacting multiple end-capping agents, multiple different end groups can be introduced.

[0541] - Acrylimization rate (ring-closure rate) -

[0542] From the perspective of the obtained organic membrane strength and insulation, a polyimide amide ratio (also known as "ring-closing ratio") of 70% or higher is preferred, 80% or higher is even better, and 90% or higher is even better.

[0543] There is no specific upper limit to the aceimide rate mentioned above, as long as it is below 100%.

[0544] The aceimide content mentioned above can be determined, for example, by the following method.

[0545] The infrared absorption spectrum of polyimide was measured, and the peak intensity P1, approximately 1377 cm⁻¹, was determined as the absorption peak originating from the amide structure. 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 P2, also approximately 1377 cm⁻¹. Using the obtained peak intensities P1 and P2, the amide content of the polyimide can be calculated according to the following formula.

[0546] Acrylimization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0547] Polyimide may contain all repeating units represented by formula (4) above, including one type of R131 or R132, or it may contain two or more different types of repeating units represented by R131 or R132 above. Furthermore, polyimide may contain other types of repeating units besides those represented by formula (4) above. Examples of other types of repeating units include those represented by formula (2) above.

[0548] Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with a diamine (a capping agent partially replaced by a monoamine) at low temperature; by reacting tetracarboxylic dianhydride (a capping agent partially replaced by an anhydride, a monochloride compound, or a monoactive ester compound) with a diamine at low temperature; by obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (a capping agent partially replaced by a monoamine) in the presence of a condensing agent; using... Polyamide precursors can be obtained by methods such as obtaining a diester from a tetracarboxylic acid dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid and reacting it with a diamine (a capping agent partially replaced by a monoamine), and then completely amide-imidizing it using a known amide-imidization reaction; or by stopping the amide-imidization reaction midway and introducing a partial amide structure; and by introducing a partial amide structure by mixing a fully amide-imidized polymer with the polyamide precursor. Furthermore, other known methods for synthesizing polyamides can also be applied.

[0549] The weight-average molecular weight (Mw) of polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or higher, the folding resistance of the cured film can be improved. For obtaining organic films with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or higher is particularly preferred.

[0550] Furthermore, 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.

[0551] The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of the polyimide; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred.

[0552] Furthermore, when the resin composition includes multiple polyimides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polyimide are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility calculated using the multiple polyimides as a single resin are within the aforementioned ranges.

[0553] Polybenzo[ [Azole precursor]

[0554] Regarding the polystyrene used in this invention The structure of the azole precursor is not specifically defined, but it is preferred to include the repeating unit represented by the following formula (3).

[0555] [Chemical Formula 14]

[0556] In formula (3), R121 represents a divalent organic group, R122 represents a tetravalent organic group, and R123 and R124 represent hydrogen atoms or monovalent organic groups, respectively.

[0557] In equation (3), R123 and R124 have the same meaning as R113 in equation (2), and the preferred range is also the same. That is, it is preferred that at least one of them is a polymeric group.

[0558] In formula (3), R121 represents a divalent organic group. Preferably, the divalent organic group comprises at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. Preferably, R121 is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

[0559] As dicarboxylic acid residues, dicarboxylic acid residues containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, with dicarboxylic acid residues containing aromatic groups being even more preferred.

[0560] As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is even more preferred. The straight-chain or branched (preferably straight-chain) aliphatic group preferably has 2 to 30 carbon atoms, 2 to 25 is more preferred, 3 to 20 is further preferred, 4 to 15 is even more preferred, and 5 to 10 is particularly preferred. The straight-chain aliphatic group is preferably an alkyl group.

[0561] Examples of dicarboxylic acids containing a straight-chain 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, etc. -Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic 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, henodecanedioic acid, docosanedioic acid, trisicosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, hexadecanedioic acid, triacontanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

[0562]

[0563] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0564] As a dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids containing only an aromatic group and two -COOH groups are even more preferred.

[0565] [Chemical Formula 16]

[0566] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * represents the bonding site with other structures independently.

[0567] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and phthalic acid.

[0568] In equation (3), R122 represents a tetravalent organogroup. As a tetravalent organogroup, it has the same meaning as R115 in equation (2) above, and the preferred range is also the same.

[0569] R122 is preferably a group derived from a diaminophenol derivative. Examples of groups derived from diaminophenol 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, and 2,2-bis-(3- Diaminophenols include (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, and 1,3-diamino-4,6-dihydroxybenzene. These diaminophenols can be used alone or in combination.

[0570] Among diaminophenol derivatives, the following diaminophenol derivatives having aromatic groups are preferred.

[0571]

[0572] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, with hydrogen atom or hydrocarbon group being preferred, and hydrogen atom or alkyl group being even more preferred. Furthermore, R122 is also preferred for the structure represented by the above formula. When R122 has the structure represented by the above formula, it is preferable that any two of the four asterisks and # are bonded to the nitrogen atom bonded to R122 in formula (3) and the other two are bonded to the oxygen atom bonded to R122 in formula (3). It is even more preferable that two asterisks are bonded to the oxygen atom bonded to R122 in formula (3) and two # are bonded to the nitrogen atom bonded to R122 in formula (3). It is even more preferable that two asterisks are bonded to the nitrogen atom bonded to R122 in formula (3) and two # are bonded to the oxygen atom bonded to R122 in formula (3). It is even more preferable that two asterisks are bonded to the oxygen atom bonded to R122 in formula (3) and two # are bonded to the nitrogen atom bonded to R122 in formula (3).

[0573] The diaminophenol derivatives represented by formula (As) are also preferred.

[0574]

[0575] In formula (As), R1 is an organogroup selected from hydrogen atom, alkyl group, substituted alkyl group, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the group consisting of the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl group, alkoxy group, acetoxy group, or cyclic alkyl group, which may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl group, alkoxy group, acetoxy group, or cyclic alkyl group, which may be the same or different.

[0576]

[0577] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0578] In the above formula (As), it is believed that having a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3, will bring the carbonyl carbon of the amide bond closer to the hydroxyl group, which is particularly good in terms of further improving the effect of achieving a high cyclization rate when hardening at low temperature.

[0579] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it can maintain high transparency to i-rays and achieve a high cyclization rate when hardened at low temperature, which is therefore better.

[0580] Furthermore, in the above formula (As), it is even more preferable that R1 is an alkylene group or a substituted alkylene group. Specific examples of alkylene groups and substituted alkylene groups of R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, polystyrene exhibits an excellent balance between maintaining high transparency to i-rays and high cyclization rate during low-temperature curing, while also achieving sufficient solubility in solvents. Regarding azole precursors, -CH2-, -CH(CH3)-, and -C(CH3)2- are preferred.

[0581] As for the method of manufacturing the diaminophenol derivative represented by the above formula (As), for example, you can refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated into this specification.

[0582] Specific examples of the structures of diaminophenol derivatives represented by the above formula (As) can be found in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and such contents are incorporated herein by reference. Of course, it is self-evident that this is not the only possible embodiment.

[0583] Polybenzo[ In addition to the repeating unit in formula (3) above, azole precursors may also contain other types of repeating units.

[0584] In terms of suppressing warpage associated with ring closure, polystyrene... It is preferable that the azole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0585] [Chemical Formula 20]

[0586] In formula (SL), Z has an a structure and a b structure. R1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R2s is a hydrocarbon group with 1 to 10 carbon atoms, at least one of R3s, R4s, R5s, and R6s is an aromatic group, and the rest are hydrogen atoms or organic groups with 1 to 30 carbon atoms. These groups can be the same or different. The polymerization of the a structure and the b structure can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a structure is 5 to 95 molars, the b structure is 95 to 5 molars, and a+b is 100 molars.

[0587] In formula (SL), Z is preferably represented by R5s and R6s in structure b being phenyl. Furthermore, the molecular weight of the structure shown in formula (SL) is preferably 400-4,000, and more preferably 500-3,000. By setting the molecular weight within the above range, the molecular weight of polystyrene can be reduced more effectively. The elastic modulus of the azole precursor after dehydration and ring closure can achieve both the effect of suppressing warpage and improving solvent solubility.

[0588] In cases where the diamine residue represented by formula (SL) is used as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. As an example of such a tetracarboxylic acid residue, R115 in formula (2) can be cited.

[0589] Polybenzo[ The weight-average molecular weight (Mw) of the azole 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.

[0590] The above polybenzo[a] A molecular weight dispersion of 1.4 or higher for the azole precursor is preferred, 1.5 or higher is even better, and 1.6 or higher is further preferred. (Polybenzoxylene) There is no specific upper limit for the molecular weight dispersion of azole precursors. For example, 2.6 or less is preferred, 2.5 or less is even better, 2.4 or less is further preferred, 2.3 or less is even more preferred, and 2.2 or less is even more preferred.

[0591] Furthermore, in resin compositions containing multiple types of polystyrene... When the azole precursor is used as a specific resin, at least one polybenzo[a]azole precursor is used. The weight-average molecular weight, number-average molecular weight, and dispersibility of the azole precursor are preferably within the above-mentioned ranges. Furthermore, the above-mentioned plurality of polyphenylene oxides... The weight-average molecular weight, number-average molecular weight, and dispersibility of the azole precursor as a single resin are also preferably within the above-mentioned ranges.

[0592] Polybenzo[ [azole]

[0593] As polystyrene azole, as long as it has benzo[a] There are no particular limitations on the polymeric compounds with an azole ring, but compounds represented by formula (X) are preferred, and compounds represented by formula (X) that have a polymerizable group are even more preferred. As the polymerizable group, a free radical polymerizable group is preferred. Alternatively, compounds represented by formula (X) that have a polar conversion group such as an acid-decomposing group may also be used.

[0594]

[0595] In formula (X), R133 represents a divalent organic group and R134 represents a tetravalent organic group.

[0596] In the case of having a polar conversion group such as a polymerizable group or an acid-degradable group, the polar conversion group such as a polymerizable group or an acid-degradable group can be located on at least one of R133 and R134, as shown in formula (X-1) or formula (X-2) below, or it can be located on polyphenylene. The terminal of the azole.

[0597]

[0598] In formula (X-1), at least one of R135 and R136 is a polar conversion group such as a polymerizable group or an acid-decomposable group, and is an organic group if it is not a polymerizable group or an acid-decomposable group. The other groups have the same meaning as in formula (X).

[0599]

[0600] In formula (X-2), R137 is a polar conversion group such as a polymerizable group or an acid-degradable group, and the others are substituents. The meanings of the other groups are the same as those in formula (X).

[0601] The polar conversion groups, such as polymerizable groups or acid-degradable groups, have the same meaning as the polymerizable groups described in the above-mentioned polyimide precursors.

[0602] R133 indicates a divalent organogroup. Examples of divalent organogroups include aliphatic and aromatic groups. A specific example is polybenzo[a]benzene. An example of R121 in formula (3) of azole precursors. Also, a preferred example is the same as R121.

[0603] R134 represents a tetravalent organogroup. Examples of tetravalent organogroups include polyphenylene oxide (PPO). An example of R122 in formula (3) of azole precursors. Also, a preferred example is the same as R122.

[0604] For example, the four bond groups of the tetravalent organogroup exemplified as R122 bond with the nitrogen and oxygen atoms in formula (X) above to form a condensation ring. For example, when R134 is the organogroup described below, the following structure is formed. In the following structures, * indicates the bonding sites with the nitrogen or oxygen atoms in formula (X), respectively.

[0605]

[0606] Polybenzo[ azole An azoleization rate of 85% or higher is preferred, and 90% or higher is even better. There is no specific upper limit; it can be 100%. Through... The azoleization rate is over 85%, achieved through heating. The membrane contraction caused by the closed ring during azoleization is reduced, thereby more effectively inhibiting warpage.

[0607] The above The azoleization rate can be determined, for example, by the following methods.

[0608] Determination of polyphenylene The infrared absorption spectrum of azole was analyzed, and the peak intensity Q1 of the amide structure, derived from the precursor, at approximately 1650 cm⁻¹ was determined. Then, the absorption intensity was normalized to that of the aromatic ring found at approximately 1490 cm⁻¹. This polyphenylene oxide... After heat treatment at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity Q2 at approximately 1650 cm⁻¹ was determined. This was then normalized to the absorption intensity of the aromatic ring observed at approximately 1490 cm⁻¹. Using the obtained standard values ​​of peak intensities Q1 and Q2, the poly(phenylene oxide) can be calculated according to the following formula. azole Azoxylation rate.

[0609] Azoxylation rate (%) = (Standard value of peak intensity Q1 / Standard value of peak intensity Q2) × 100

[0610] Polybenzo[ Azoles may contain only repeating units of formula (X) of the above type, including one type of R131 or R132, or they may contain repeating units of formula (X) of the above type, including two or more different types of R131 or R132. Furthermore, polybenzo[…] In addition to the repeating units in the above formula (X), azoles may also contain other types of repeating units.

[0611] Regarding polyphenylene azoles, for example, are obtained by reacting a diaminophenol derivative with a dicarboxylic acid containing R133, or a dicarboxylic acid dichloride selected from the dicarboxylic acid and dicarboxylic acid derivatives. Azole precursors, and utilizing known... Azolization reaction method to make It is obtained by azoleization.

[0612] In addition, in the case of dicarboxylic acids, in order to improve the reaction yield, an active ester-type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole can be used.

[0613] Polybenzo[ The weight-average molecular weight (Mw) of the azole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. Setting the weight-average molecular weight to 5,000 or higher improves the folding resistance of the cured film. For organic films with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, in the presence of two or more polybenzo[a]azoles... In the case of azole, at least one polybenzo[a] The weight-average molecular weight of azoles is preferably within the above-mentioned range.

[0614] Also, polyphenylene The number average molecular weight (Mn) of the azole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0615] The above polybenzo[a] A molecular weight dispersion of azole of 1.4 or higher is preferred, 1.5 or higher is even better, and 1.6 or higher is further preferred. Polybenzo[a] There is no specific upper limit for the molecular weight dispersity of azoles. For example, 2.6 or less is preferred, 2.5 or less is even better, 2.4 or less is further preferred, 2.3 or less is further preferred, and 2.2 or less is even more preferred.

[0616] Furthermore, in resin compositions containing multiple types of polystyrene... In the case of azole as a specific resin, at least one polybenzoxylene... The weight-average molecular weight, number-average molecular weight, and dispersibility of azoles are preferably within the above-mentioned ranges. Furthermore, the above-mentioned plurality of polyphenylene oxides... The weight-average molecular weight, number-average molecular weight, and dispersity of azole as a resin are also better within the above ranges.

[0617] [Polyamide imine precursor]

[0618] It is preferable that the polyamide imide precursor contains repeating units represented by the following formula (PAI-2).

[0619]

[0620] In formula (PAI-2), R117 represents a trivalent organic group, R111 represents a divalent organic group, A2 represents an oxygen atom or -NH-, and R113 represents a hydrogen atom or a monovalent organic group.

[0621] In formula (PAI-2), R117 can be an example of a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups by a single bond or by a linking group. It is preferred to obtain a group obtained by combining two or more of these groups by a straight-chain aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or by combining two or more of these groups by a single bond or by a linking group. It is even more preferred to obtain a group obtained by combining two or more of these groups by a single bond or by combining two or more of these groups by a linking group by an aromatic group with 6 to 20 carbons.

[0622] As the linking group mentioned above, it is preferred to form a linking group consisting of -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds, and it is even more preferred to form a linking group consisting of -O-, -S-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds.

[0623] As the aforementioned alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

[0624] As the aforementioned alkyl halides, alkyl halides with 1 to 20 carbon atoms are preferred, alkyl halides with 1 to 10 carbon atoms are more preferred, and alkyl halides with 1 to 4 carbon atoms are even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halides include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The aforementioned alkyl halides may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution of all hydrogen atoms with halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene.

[0625] As described above, aryl, phenyl or naphthyl are preferred, phenyl is more preferred, and 1,3-phenyl or 1,4-phenyl are even more preferred.

[0626] Furthermore, R117 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. Chlorination is preferred as the halogenation method described above.

[0627] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0628] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0629] Examples of tricarboxylic acid compounds that can be halogenated and used in the manufacture of polyamide imine precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0630] These tricarboxylic acid compounds may be used in single or multiple forms.

[0631] Specifically, as a tricarboxylic acid compound, a tricarboxylic acid compound comprising a straight-chain 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 single bond or a group obtained by combining two or more of these groups via a linker is preferred. A tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a linker is even more preferred.

[0632] Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or extended phenyl groups.

[0633] These compounds can be compounds in which two carboxyl groups are anhydride-substituted (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride chloro).

[0634] In formula (PAI-2), R111, A2, and R113 have the same meaning as R111, A2, and R113 in formula (2) above, and the better state is also the same.

[0635] Polyamide imine precursors may further include other repeating units.

[0636] Other repeating units can be exemplified by the repeating unit represented by equation (2) above, the repeating unit represented by equation (PAI-1) below, etc.

[0637]

[0638] In formula (PAI-1), R116 represents a divalent organic group, and R111 represents a divalent organic group.

[0639] In formula (PAI-1), R116 can be an example of a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups by a single bond or by a linking group. It is preferred to obtain a group obtained by combining two or more of these groups by a straight-chain aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or by combining two or more of these groups by a single bond or by a linking group. It is even more preferred to obtain a group obtained by combining two or more of these groups by a single bond or by combining two or more of these groups by a linking group by an aromatic group with 6 to 20 carbons.

[0640] As the linking group mentioned above, it is preferred to form a linking group consisting of -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds, and it is even more preferred to form a linking group consisting of -O-, -S-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds.

[0641] As the aforementioned alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

[0642] As the aforementioned alkyl halides, alkyl halides with 1 to 20 carbon atoms are preferred, alkyl halides with 1 to 10 carbon atoms are more preferred, and alkyl halides with 1 to 4 carbon atoms are even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halides include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The aforementioned alkyl halides may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution of all hydrogen atoms with halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene.

[0643] As described above, aryl, phenyl or naphthyl are preferred, phenyl is more preferred, and 1,3-phenyl or 1,4-phenyl are even more preferred.

[0644] Furthermore, it is preferable that R116 is derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0645] In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide.

[0646] In dicarboxylic acid dihalides, the carboxyl group only needs to be halogenated, for example, chlorination is preferred. That is, dicarboxylic acid dihalides are preferably dicarboxylic acid dichloride compounds.

[0647] Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that can be halogenated and used in the manufacture of polyamide imine precursors include linear or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0648] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in a single form or in two or more forms.

[0649] Specifically, as a dicarboxylic acid compound or dicarboxylic acid dihalide, it is preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide contains a straight-chain 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 single bond or a group obtained by combining two or more of these groups via a linking group. It is even more preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide contains an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a linking group.

[0650] Furthermore, specific examples of dicarboxylic acid compounds 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, di Decanedioic acid, hexadecanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic 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.

[0651] As a specific example of a dicarboxylic acid dihalide, a compound with a structure formed by halogenating two carboxyl groups in the above-mentioned dicarboxylic acid compound examples can be cited.

[0652] In formula (PAI-1), R111 has the same meaning as R111 in formula (2) above, and the better state is also the same.

[0653] Furthermore, it is preferable that the polyamide imide precursor contains fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyamide imide precursor is 10% by mass or more, and 20% by mass or less.

[0654] Furthermore, to improve adhesion to the substrate, the polyamide imine precursor can be copolymerized with an aliphatic group having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0655] As one embodiment of the polyamide imide precursor of the present invention, an example is provided where the total content of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is particularly preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2).

[0656] Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, an example is provided where the total content of the repeating units represented by formula (PAI-2) and formula (PAI-1) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is particularly preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2) or formula (PAI-1).

[0657] The weight-average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, 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.

[0658] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of the polyamide-imide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred. Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyamide-imide precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when considering the multiple polyamide-imide precursors as a single resin are within the above-mentioned ranges.

[0659] [Polyamide-Imine]

[0660] The polyamide used in this invention can be an alkali-soluble polyamide or a polyamide that is soluble in a developer solution with organic solvents as the main component.

[0661] In this specification, alkali-soluble polyamide-imide refers to polyamide-imide that dissolves at least 0.1 g in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From a pattern-forming point of view, dissolving at least 0.5 g of polyamide-imide is preferred, and dissolving at least 1.0 g of polyamide-imide is further preferred. There is no particular upper limit to the above dissolution amount, but less than 100 g is preferred.

[0662] Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyamide-amide imide with a plurality of amide bonds and a plurality of amide structures on the main chain is preferred.

[0663] -Fluorine atom-

[0664] From the perspective of the strength of the obtained organic membrane, polyamide imide with fluorine atoms is preferred.

[0665] It is preferable that the fluorine atom is included, for example, in R117 or R111 of the repeating unit represented by the following formula (PAI-3), and it is even more preferable that it is included as a fluorinated alkyl group in R117 or R111 of the repeating unit represented by the following formula (PAI-3).

[0666] The amount of fluorine atoms relative to the total mass of polyamide imide is preferably 5% by mass or more, and preferably less than 20% by mass.

[0667] -Ethylene unsaturated bond-

[0668] From the perspective of the membrane strength of the obtained organic membrane, polyamide imine can have vinyl unsaturated bonds.

[0669] Polyamide imides can have ethylene unsaturated bonds at the end of the main chain or on the side chain, but it is better to have ethylene unsaturated bonds on the side chain.

[0670] The aforementioned ethylene-type unsaturated bonds exhibit better free radical polymerization properties.

[0671] It is preferable that the ethylene unsaturated bond is contained in R117 or R111 of the repeating unit represented by the following formula (PAI-3), and it is even more preferable that the group having the ethylene unsaturated bond is contained in R117 or R111 of the repeating unit represented by the following formula (PAI-3).

[0672] The preferred state of the polyimide having vinyl unsaturated groups is the same as the preferred state of the polyimide having vinyl unsaturated groups described above.

[0673] The amount of vinyl unsaturated bonds relative to the total mass of polyamide imide is preferably 0.0001~0.1 mol / g, and even more preferably 0.001~0.05 mol / g.

[0674] -Polymerizable groups other than ethylene unsaturated bonds-

[0675] Polyamide imides can have polymerizable groups other than ethylene unsaturated bonds.

[0676] As a polymerizable group in polyamide imine other than the vinyl unsaturated bond, the same group as the polymerizable group in the polyamide imine mentioned above can be cited.

[0677] It is preferable that polymerizable groups other than ethylene unsaturated bonds are included, for example, in R111 of the repeating unit represented by the formula (PAI-3) described later.

[0678] The amount of polymeric groups other than ethylene unsaturated bonds relative to the total mass of polyamide imide is preferably 0.05~10 mol / g, and even more preferably 0.1~5 mol / g.

[0679] -Polar conversion group-

[0680] Polyamide imides can have polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyamide imides are the same as those described in R113 and R114 in the above formula (2), and the preferred state is also the same.

[0681] -Acid Value-

[0682] When polyamide is used for alkaline development, from the viewpoint of improving developability, the acid value of polyamide is preferably 30 mg KOH / g or higher, 50 mg KOH / g or higher is even better, and 70 mg KOH / g or higher is even more better.

[0683] Furthermore, an acid value of 500 mg KOH / g or less is preferred, 400 mg KOH / g or less is even better, and 200 mg KOH / g or less is even more preferred.

[0684] Furthermore, when polyamide imide is used in developing solutions that are primarily composed of organic solvents (e.g., "solvent development" as described below), the acid value of polyamide imide is preferably 2 to 35 mg KOH / g, more preferably 3 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0685] The acid value mentioned above is determined by known methods, such as the method described in JIS K 0070:1992.

[0686] Furthermore, as for the acid groups contained in polyamide imide, groups that are the same as the acid groups in the aforementioned polyamide imide can be cited, and the preferred state is also the same.

[0687] -Phenolic hydroxyl-

[0688] From the viewpoint of making the development speed of alkaline developer suitable, polyamide imine with phenolic hydroxyl groups is preferred.

[0689] Polyamide imine can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0690] It is preferable that the phenolic hydroxyl group is included, for example, in R117 or R111 of the repeating unit represented by the following formula (PAI-3).

[0691] The amount of phenolic hydroxyl groups relative to the total mass of polyamide imine is preferably 0.1~30 mol / g, and even more preferably 1~20 mol / g.

[0692] The polyamide amide used in this invention is not particularly limited as long as it is a polymer compound having an amide structure and amide bonds, but it is preferred to include repeating units represented by the following formula (PAI-3).

[0693] [Chemical Formula 27]

[0694] In formula (PAI-3), R111 and R117 have the same meaning as R111 and R117 in formula (PAI-2), and the better state is also the same.

[0695] In the case of having a polymerizable group, the polymerizable group can be located on at least one of R111 and R117, or it can be located at the end of the polyamide imide.

[0696] Furthermore, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamide amide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorinated compounds, or monoactive ester compounds. The preferred state of the end-capping agent is the same as that of the end-capping agents in the polyamides mentioned above.

[0697] - Acrylimization rate (ring-closure rate) -

[0698] From the perspective of the obtained organic membrane strength and insulation, a polyamide ...

[0699] There is no specific upper limit to the aceimide rate mentioned above, as long as it is below 100%.

[0700] The amide ratio was determined using the same method as the ring-closing ratio of the polyamide.

[0701] Polyamide imides may contain only repeating units represented by the above formula (PAI-3) including one type of R111 or R117, or they may contain repeating units represented by the above formula (PAI-3) including two or more different types of R131 or R132. Furthermore, polyamide imides may contain other types of repeating units besides those represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0702] Polyamide imides can be synthesized, for example, by methods such as obtaining a polyamide imide precursor by known methods and fully imidizing it using a known imidization reaction; or by stopping the imidization reaction midway and introducing a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyamide imide precursor.

[0703] The weight-average molecular weight (Mw) of polyamide amide 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 higher, the folding resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred.

[0704] Furthermore, the number average molecular weight (Mn) of the polyamide imine is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0705] The molecular weight dispersion of polyamide amide is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of polyamide amide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and further preferably 6.0 or lower.

[0706] Furthermore, when the resin composition includes multiple polyamides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide is within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyamides as a single resin are within the aforementioned ranges.

[0707] [Methods for manufacturing polyimide precursors, etc.]

[0708] Polyimide precursors can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature; by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide and then esterifying it with a condensing agent or alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine. Among the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine is preferred.

[0709] Examples of condensing agents mentioned above 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.

[0710] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0711] Examples of halogenating agents mentioned above include thiocyanate, oxalic acid, and phosphorus oxychloride.

[0712] In methods for manufacturing polyimide precursors, it is preferable to use an organic solvent during the reaction. The organic solvent can be one type or two or more types.

[0713] As an organic solvent, it can be appropriately selected according to the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0714] In methods for manufacturing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound can be one type or two or more types.

[0715] The basic compound can be appropriately set according to the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0716] -End- Capping Agent-

[0717] In methods for manufacturing polyimide precursors, etc., it is preferable to seal the carboxylic anhydride, anhydride derivatives, or amine groups remaining at the resin ends of the polyimide precursor, etc., to further improve storage stability. When sealing the carboxylic anhydride and anhydride derivatives remaining at the resin ends, monohydric alcohols, phenols, thiols, benzenethiophenols, monoamines, etc., can be used as sealing agents. From the viewpoint of reactivity and film stability, monohydric alcohols, phenols, or monoamines are preferred. Preferred compounds as monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tertiary alcohols such as butanol and adamantanol. Preferred compounds among phenols include phenols, methoxyphenols, methylphenols, naphth-1-ols, naphth-2-ols, and hydroxystyrene. Preferred compounds among monoamines 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, and 1-carboxy-5-aminonaphthalene. Naphthalene, 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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and by reacting multiple end-capping agents, multiple different end groups can be introduced.

[0718] Furthermore, when sealing the amine groups at the end of the resin, compounds with functional groups capable of reacting with the amine groups can be used for sealing. Preferred sealants for amine groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norcamphene-2,3-dicarboxylic anhydride. Furthermore, preferred compounds as carboxylic acid chlorides include acetyl chloride, acrylamide chloride, propionyl chloride, methacrylamide chloride, trimethylacetyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamic acid chloride, 1-adamantanemethyl chloride, heptafluorobutyric acid chloride, stearic acid chloride, and benzyl chloride.

[0719] -Solid precipitation-

[0720] In the manufacture of polyimide precursors, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer components are added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, causing the polymer components to precipitate as a solid and then dried, thereby obtaining the polyimide precursor. To improve the purification degree, the operations of re-dissolving, re-precipitating, and drying the polyimide precursor may be repeated. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[0721] 〔content〕

[0722] The content of a specific resin in the resin composition of the present invention is preferably 20% by mass or more relative to the total solid content of the resin composition, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0723] The resin composition of the present invention may contain only one specific resin, or it may contain two or more resins. When two or more resins are contained, it is preferable that the total amount is within the above-mentioned range.

[0724] Furthermore, it is preferable that the resin composition of the present invention contains at least two resins.

[0725] Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or it may contain two or more specific resins, but it is preferred to contain two or more specific resins.

[0726] In the case where the resin composition of the present invention contains two or more specific resins, it is preferable to contain two or more polyimide precursors that are polyimide precursors and are derived from different structures of dianhydrides (R115 described in formula (2) above).

[0727] <Other Resins>

[0728] The resin composition of the present invention may include other resins (hereinafter also referred to as "other resins") that are different from a specific resin.

[0729] Furthermore, it can also be configured to include a specific resin and other resins.

[0730] Other resins include phenolic resins, polyamides, epoxy resins, resins containing polysiloxane or siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, amine resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0731] For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

[0732] For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a (meth)acrylic resin with a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1×10-3 moles / g or more) with a weight average molecular weight of 20,000 or less can be added to the resin composition, thereby improving the coatability of the resin composition, the solvent resistance of the pattern (cured material), etc.

[0733] When the resin composition of the present invention includes other resins, it is preferable that the content of other resins is 0.01% by mass or more relative to the total solid content of the resin composition, more preferably 0.05% by mass or more, further preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0734] When the resin composition of the present invention does not contain a specific resin, it is preferable that the content of other resins is 20% by mass or more relative to the total solid content of the resin composition, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, it is preferable that the content of resin in the resin composition of the present invention is 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0735] Furthermore, when the resin composition of the present invention includes a specific resin and other resins, it is preferable that the content of the other resins is 80% by mass or less relative to the total solid content of the resin composition, more preferably 75% by mass or less, further preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and it can also be set to 40% by mass or less, and further preferably 30% by mass or less.

[0736] Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to provide an embodiment containing a specific resin and with other resins present in low amounts. In the above-mentioned embodiment, it is preferable that the content of other resins relative to the total solids content of the resin composition is 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0737] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When two or more other resins are contained, it is preferable that the total amount is within the above-mentioned range.

[0738] Among these, it is preferable that the resin composition of the present invention comprises at least one resin selected from the group consisting of specific resins, phenolic resins and epoxy resins.

[0739] As a phenolic resin, it can be either a soluble phenolic resin or a phenolic varnish. Specifically, examples include cresol phenolic varnish resin, catechol phenolic varnish resin, resorcinol phenolic varnish resin, hydroquinone phenolic varnish, catechol-resorcinol phenolic varnish resin, and resorcinol-hydroquinone phenolic varnish resin.

[0740] There are no particular limitations on epoxy resins, but examples include phenolic varnish-type epoxy resins, bisphenol-type epoxy resins, glycidyl amine-type epoxy resins, glycidyl ether-type epoxy resins, pyrrolidone-methane-type epoxy resins, pyrrolidone-propane-type epoxy resins, alkyl-modified pyrrolidone-methane-type epoxy resins, and epoxy resins containing triphenols. The epoxy resins include nuclear epoxy resins, dicyclopentadiene-modified phenolic epoxy resins, naphthol epoxy resins, naphthalene epoxy resins, phenolic aralkyl epoxy resins having at least one of the extended phenyl skeleton and the biphenyl-like skeleton, naphthol aralkyl epoxy resins having at least one of the extended phenyl skeleton and the biphenyl-like skeleton, and aliphatic epoxy resins.

[0741] <Polymerizing compounds>

[0742] The resin composition of the present invention preferably contains a polymeric compound.

[0743] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0744] Furthermore, it is preferable that the resin composition of the present invention (especially the second resin composition) contains a compound having an aromatic polycyclic structure.

[0745] It is preferable that the second resin composition, which has wiring (such as copper) disposed on it, possesses properties that improve the electrical performance of the wiring, and is in direct contact with the wiring, for example, it is preferable that the second resin composition has a low dielectric constant. Therefore, it is preferable that the compounds contained in the second resin composition have aromatic polycyclic structures such as fumonisin skeleton and polystyrene skeleton, fluorinated monomers such as 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-(hexafluoroisopropylidene)phthalic anhydride, or siloxanes derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc., and have a relative dielectric constant of less than 3.0 when forming a film from themselves, more preferably less than 2.8, and further preferably less than 2.6. The lower limit of the above relative dielectric constant is not particularly limited, as long as it is 0 or above.

[0746] When the film is formed from the above compounds, it is preferable that the dielectric loss tangent is 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less. There is no particular limitation on the lower limit of the dielectric loss tangent, as long as it is 0 or more.

[0747] Therefore, it is preferable that the second resin composition contains a compound having a polymeric group and an aromatic polycyclic structure, and even more preferable that it contains a compound having a polymeric group and a fusiform skeleton.

[0748] Preferably, the dielectric constant of the above-mentioned compound is less than that of the resin and / or its precursor contained in the second resin composition.

[0749] Specifically, it is preferable that the difference between the dielectric constant of the film formed from the above-mentioned resin and the relative dielectric constant of the film formed from the above-mentioned compound is 0.2 or more, and even more preferably 0.4 or more.

[0750] The aromatic group in a polymeric compound containing an aromatic group can be monocyclic or polycyclic, but polycyclic is preferred, and condensed ring is even better.

[0751] Examples of polycyclic aromatic ring structures include biphenyl structures, triphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fumonisin ring structures, acenaphthene ring structures, etc., but are not limited to these.

[0752] [Free radical crosslinking agent]

[0753] It is preferable that the resin composition of the present invention contains a free radical crosslinking agent.

[0754] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, the free radical polymerizable group contains an ethylene unsaturated bond. Examples of such ethylene unsaturated bond groups include vinyl, allyl, vinylphenyl, (meth)acryl, maleicadiimino, and (meth)acrylamine groups.

[0755] Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the groups containing vinyl unsaturated bonds, and (meth)acryl is more preferred from the viewpoint of reactivity.

[0756] Free radical crosslinking agents are preferably compounds with one or more vinyl unsaturated bonds, but compounds with two or more are even more preferred. Free radical crosslinking agents can have three or more vinyl unsaturated bonds.

[0757] As for the compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are even more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred.

[0758] Furthermore, from the viewpoint of the film strength of the obtained pattern (hardened material), it is preferable that the resin composition of the present invention contains compounds having two ethylene unsaturated bonds and the aforementioned compounds having three or more ethylene unsaturated bonds.

[0759] The molecular weight of the free radical crosslinking agent is preferably below 2,000, more preferably below 1,500, and even more preferably below 900. The lower limit of the molecular weight of the free radical crosslinking agent is preferably above 100.

[0760] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, it is also preferable to use addition reactions of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl or amino groups, or hydrogen sulfide groups, with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyl groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Additionally, as another example, compounds that replace the aforementioned unsaturated carboxylic acids can be used, such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and such contents are incorporated into this specification.

[0761] Furthermore, it is preferable that the free radical crosslinking agent is a compound with a boiling point above 100°C at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetra(meth)acrylate, neopentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloxypropyl) ether, tri(acryloxyethyl)isocyanurate, glycerol, or trimethylolethane, which are added to polyfunctional alcohols to form ethylene oxide or propylene oxide, followed by (methyl) crosslinking. Compounds obtained by esterification of acrylic acid, such as (meth)acrylate amino esters described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, and polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, as well as epoxy acrylates and other multifunctional acrylates or methacrylates as products of the reaction between epoxy resin and (meth)acrylic acid, and mixtures thereof. Furthermore, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Alternatively, examples include polyfunctional (meth)acrylates obtained by reacting compounds such as glycidyl (meth)acrylate, which have cyclic ether groups and vinyl unsaturated bonds, with polyfunctional carboxylic acids.

[0762] Furthermore, as a preferred free radical crosslinking agent besides the above, compounds having a cycloid and having two or more groups containing ethylene unsaturated bonds, or cardo resins, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

[0763] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can also be used. Additionally, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0764] In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be used more readily, and such contents are incorporated into this specification.

[0765] Furthermore, in Japanese Patent Application Publication No. 10-062986, the following compound, which is described together with specific examples as formula (1) and formula (2), can also be used as a free radical crosslinking agent. This compound is obtained by (meth)acrylate esterification after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0766] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

[0767] As free radical crosslinking agents, dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and structures in which the (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0768] Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four ethynooxy chains) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (difunctional methyl acrylates with four ethoxy chains) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentynooxy chains) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isobutyryloxy chains); amine ester oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku). Co., Ltd. manufactures UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (and above, manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0769] As free radical crosslinking agents, amine ester acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and amine ester compounds with an ethylene oxide backbone described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0770] Free radical crosslinking agents can be those containing acid groups such as carboxyl or phosphate groups. It is preferable that the free radical crosslinking agent containing acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. It is even more preferable that the free radical crosslinking agent containing acid groups is formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent containing acid groups formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl tetrol or dinepentyl tetrol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., such as M-510 and M-520.

[0771] As described above, it is preferable that the resin composition of the present invention (especially the second resin composition) contains a polymerizable compound having an aromatic polycyclic structure as the polymerizable compound.

[0772] Examples of free radical crosslinking agents with aromatic polycyclic structures include 1,3-divinylnaphthalene, acenaphthene, 9,9-bis[4-[2-(acryloyloxy)ethoxy]phenyl]-9H-fu, 9,9-bis[4-[2-[2-(acryloyloxy)ethoxy]ethoxy]phenyl]-9H-fu, and compounds with the following structures.

[0773]

[0774] Commercially available products include, for example, those manufactured by Osaka Gas Chemicals Co., LTD., such as OGSOL CG-500, EA-0200, EA-300, GA-2800, GA-5000, GA-5060P, EA-F5710, and EA-HR033.

[0775] The preferred acid value of a free radical crosslinking agent containing an acid group is 0.1~300 mg KOH / g, and the particularly preferred acid value is 1~100 mg KOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, the manufacturing process is excellent, and consequently, the developability is excellent. Furthermore, the polymerizability is good. The above acid value is determined according to the description in JIS K 0070:1992.

[0776] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition.

[0777] As specific compounds, the following can be used: triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethyloltricyclodecane diacrylate, dimethyloltricyclodecane dimethacrylate, and the EO of bisphenol A. Ethylene oxide (EO) adduct diacrylate, bisphenol A (EO) adduct dimethacrylate, bisphenol A (PO) (propylene oxide) adduct diacrylate, bisphenol A (PO) adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, cyanuric acid (EO) modified diacrylate, cyanuric acid (EO) modified dimethacrylate, difunctional acrylates having other amine ester bonds, and difunctional methacrylates having amine ester bonds. Two or more of these can be used in combination as needed.

[0778] Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain weight of approximately 200.

[0779] Regarding the resin composition of the present invention, from the viewpoint of suppressing warpage by controlling the elastic modulus of the accompanying pattern (cured material), a monofunctional free radical crosslinking agent can be preferably used as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are 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, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, alkenyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, compounds with a boiling point of over 100°C at normal pressure are preferred in order to suppress volatilization before exposure.

[0780] In addition, examples of allyl compounds, such as diallyl phthalate and trimellitic acid, can be used as free radical crosslinking agents with two or more functions.

[0781] In the case of a free radical crosslinking agent, it is preferable that its content relative to the total solids content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is further preferred.

[0782] Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more at the same time, it is better to keep the total dosage within the above range.

[0783] [Other crosslinking agents]

[0784] It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above-mentioned free radical crosslinking agents.

[0785] In this invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. It is preferable that the compound has a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the photosensitive acid generator or photobase generator mentioned above. It is also preferable that the compound has a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the action of acid or base.

[0786] It is preferable that the acid or base mentioned above is generated from the photoacid generator or photoalkali generator during the exposure step.

[0787] As other crosslinking agents, compounds having at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred.

[0788] Other crosslinking agents include, for example, compounds having a structure in which hydrogen atoms of the amine groups are replaced by acetoxymethyl, hydroxymethyl, or alkoxymethyl groups through reaction of formaldehyde or formaldehyde and alcohol with melamine, glycourea, urea, alkyl urea, benzoguanamine, or other amine-containing compounds. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Alternatively, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used.

[0789] Crosslinking agents that use melamine as the above-mentioned amine-containing compounds are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkyl urea are called urea-based crosslinking agents; crosslinking agents that use alkyl urea are called alkyl urea-based crosslinking agents; and crosslinking agents that use benzoguanidine are called benzoguanidine-based crosslinking agents.

[0790] In these respects, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and it is even more preferable that it contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0791] As a compound containing at least one of the alkoxymethyl and acetoxymethyl groups of the present invention, examples include compounds in which the alkoxymethyl or acetoxymethyl group is directly on the nitrogen atom of an aromatic group or a urea structure described below, or on a tri-atom. Compounds with top substitution are used as structural examples.

[0792] It is preferred that the alkoxymethyl or acetomethyl group in the above compounds has 2 to 5 carbon atoms, 2 or 3 carbon atoms are preferred, and 2 carbon atoms are even more preferred.

[0793] It is preferable that the total number of alkoxymethyl and aceoxymethyl groups in the above compounds is 1 to 10, more preferably 2 to 8, and especially preferably 3 to 6.

[0794] The molecular weight of the above-mentioned compounds is preferably below 1500, and 180 to 1200 is preferred.

[0795]

[0796] R100 indicates alkyl or acetylated.

[0797] R101 and R102 each represent a monovalent organic group and can bond together to form a ring.

[0798] As compounds in which alkoxymethyl or acetomethyl groups are directly substituted on an aromatic group, examples include various compounds of the following general formula.

[0799]

[0800] In the formula, X represents a single bond or a divalent organic group, each R104 independently represents an alkyl or acetyl group, and R103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to produce a base-soluble group (e.g., a group that is released under the action of an acid, or a group represented by -C(R4)2COOR5 (R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group that is released under the action of an acid.)).

[0801] R105 independently represents alkyl or alkenyl groups, a, b and c are each 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.

[0802] Regarding groups that decompose under the action of acid to produce base-soluble groups, groups that are removed under the action of acid, and R5 in the group represented by -C(R4)2COOR5, examples include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39).

[0803] In the formula, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups, respectively. R36 and R37 can bond together to form a ring.

[0804] As the aforementioned alkyl group, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 5 carbon atoms are even more preferred.

[0805] The aforementioned alkyl group can be either straight-chain or branched.

[0806] As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is even more preferred.

[0807] The aforementioned cycloalkyl groups can be monocyclic structures or polycyclic structures such as condensed rings.

[0808] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and phenyl is even more preferred.

[0809] Aryl groups with 7 to 20 carbon atoms are preferred, and aryl groups with 7 to 16 carbon atoms are even more preferred.

[0810] The aforementioned aryl group refers to an aryl group substituted with an alkyl group, and the preferred state of such alkyl and aryl groups is the same as that of the aforementioned alkyl and aryl groups.

[0811] The alkenyl group with 3 to 20 carbon atoms is preferred, and the alkenyl group with 3 to 16 carbon atoms is even more preferred.

[0812] Furthermore, these groups may also have known substituents within the scope of achieving the effects of the present invention.

[0813] R01 and R02 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups, respectively.

[0814] The groups that decompose to produce a base-soluble group by the action of an acid, or that are removed by the action of an acid, are preferably trialkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are trialkyl ester groups or acetal groups.

[0815] Specifically, the following structures can be cited as examples of compounds having an alkoxymethyl group. Regarding compounds having an acetoxymethyl group, compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group can be cited. Various compounds can be cited as examples of compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule, but the list is not limited to these.

[0816]

[0817] [Chemical Formula 32]

[0818] For compounds containing at least one of alkoxymethyl and aceoxymethyl, commercially available ones or those synthesized by known methods may be used.

[0819] From a heat resistance perspective, alkoxymethyl or aceoxymethyl groups are directly attached to the aromatic ring or trimethyl group. Compounds with ring substitutions are preferred.

[0820] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0821] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, and tetramethoxymethylated glycourea. Glycourea-based crosslinking agents, including monoethoxymethylated glycourea, diethoxymethylated glycourea, triethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea; urea-based crosslinking agents, including dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, dibutoxymethylurea; monohydroxymethylated ethoxyurea or dihydroxymethylated ethoxyurea; monomethoxymethylated ethoxyurea; dimethoxymethylated ethoxyurea; monoethoxymethylated ethoxyurea; and diethoxymethylated ethoxyurea. Urea, ethoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea or dibutoxymethylated ethoxyurea and other ethoxyurea-based crosslinking agents, monohydroxymethylated ethoxyurea, dihydroxymethylated ethoxyurea, monomethoxymethylated ethoxyurea, dimethoxymethylated ethoxyurea, monoethoxymethylated ethoxyurea, diethoxymethylated ethoxyurea, monopropoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea or dibutoxymethylated ethoxyurea and other ethoxyurea-based crosslinking agents, 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0822] Specific examples of benzoguanidine-based crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0823] In addition, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring).

[0824] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethyl phenyl ester, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenyl Methyl ketone, methoxymethylbenzoic acid methoxymethylphenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4”-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0825] Other commercially available crosslinking agents can also be used. Among the preferred commercially available agents are 46DMOC, 46DMOEP (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, DMOM-PTBP, and DMOM-MB. PC, 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.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0826] Furthermore, the resin composition of the present invention comprises a group selected from epoxy compounds, cyclobutane compounds, and benzo[a]benzene compounds. At least one compound from the group of compounds is preferred as another crosslinking agent.

[0827] -Epoxy compounds (compounds containing epoxy groups)-

[0828] As an epoxy compound, compounds having two or more epoxy groups per molecule are preferred. Epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions caused by cross-linking, thus minimizing film shrinkage. Therefore, the presence of an epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition of the present invention.

[0829] The presence of polyethylene oxide in the epoxy compound is preferred. This further reduces the elastic modulus and suppresses warpage. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, with 2 to 15 repeating units being preferred.

[0830] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkyl glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones with epoxy groups such as polymethyl(glycidyloxypropyl)siloxane, but are not limited to these. Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (these are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, and Rika... Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.)), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel) (Manufactured by Nippon Kayaku Co., Ltd.), 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 (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), DENACOL EX-614B, EX-313, EX-512, EX-321L, EX-612, EX-614, EX-622, EX-314, EX-421, EX-521, EX-411 (all manufactured by Nagase Chemtex Corporation), etc. Furthermore, the following compounds may also be used preferentially.

[0831]

[0832] In the formula, n is an integer from 1 to 5 and m is an integer from 1 to 20.

[0833] Among the above structures, considering both heat resistance and elongation, n = 1~2 and m = 3~7 are preferred.

[0834] As described above, it is preferable that the resin composition of the present invention (especially the second resin composition) contains a polymerizable compound having an aromatic polycyclic structure as the polymerizable compound.

[0835] Examples of epoxide compounds with aromatic polycyclic structures include compounds with the following structures.

[0836]

[0837] -Oxycyclic butane compounds (compounds containing oxycyclic butane groups)-

[0838] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxybutane, 1,4-bis{[(3-ethyl-3-oxocyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxocyclobutane)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. is preferred, and two or more of these can be used alone or in combination.

[0839] -Benzo Compounds (with benzo[]) (Azolium compounds)

[0840] Due to the cross-linking reaction caused by the ring-opening addition reaction, benzo[a] The compound does not degas during hardening, thereby further reducing thermal shrinkage and inhibiting warping, making it a better choice.

[0841] As benzo A preferred example of a compound could be a Pd-type benzo[a] compound. ,Fa type benzo (The above are product names, manufactured by Shikoku Chemicals Corporation), benzo[a]benzene of polyhydroxystyrene resin. Additions, phenolic varnish type dihydrobenzo[a] Compounds. These can be used alone or in combination of two or more.

[0842] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, further preferably 0.5-15% by mass, and particularly preferably 1.0-10% by mass. The other crosslinking agents may be only one type or may contain two or more types. When two or more other crosslinking agents are contained, it is preferable that their total content falls within the above-mentioned range.

[0843] [Polymerization initiator]

[0844] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it is preferable to contain a photopolymerization initiator.

[0845] Photopolymerization initiators are preferably photoradical polymerization initiators. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are photosensitizing to light in the ultraviolet to visible regions are preferred. Alternatively, it can be an activator that interacts with a photoexcited sensitizer to generate active free radicals.

[0846] The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L / mol⁻¹ / cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to use a UV-Vis spectrophotometer (Varian Medical Systems, Inc., Cary-5 spectrophotometer) and ethyl acetate solvent at a concentration of 0.01 g / L.

[0847] As photoradical polymerization initiators, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., those with trihalomethanes) can be cited. Compounds with skeletons, possessing Compounds with a diazole skeleton, compounds containing trihalomethyl groups, etc., acetyphosphine compounds such as acetyphosphine oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For details regarding these, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and these contents are incorporated herein by reference. Furthermore, examples can be cited in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, 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, and these contents are also incorporated into this specification.

[0848] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611 can be cited, and this content is incorporated into this specification. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0849] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and this content is incorporated into this specification.

[0850] As α-hydroxyketone initiators, 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, and IRGACURE 127 (all manufactured by BASF) can be used.

[0851] As α-aminoketone initiators, 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.

[0852] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is included in this specification.

[0853] Examples of phosphine oxide initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

[0854] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0855] Oxime compounds are a better example of photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds have a wider exposure latitude (exposure margin) and also act as photocuring accelerators, making them particularly advantageous.

[0856] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 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 the Journal of Photopolymer Science and... The compounds described in Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0857] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoxyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propoxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoxyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonoxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linker within the molecule.

[0858]

[0859] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, the photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, 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) are also suitable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co.,Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structures can also be used.

[0860] [Chemical Formula 36]

[0861]

[0862] Oxime compounds having a cyclohexane ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, and these contents are incorporated into this specification.

[0863] As a photoradical polymerization initiator, oxime compounds having at least one benzene ring in the carbazole ring as the naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0864] Furthermore, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, and these contents are included in this specification.

[0865] Nitro-containing oxime compounds can be used as photopolymerization initiators. It is also preferable that the nitro-containing oxime compound is a dimer. Specific examples of nitro-containing oxime compounds include the compounds described in paragraphs 0031-0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008-0012 and 0070-0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007-0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) can also be cited as a nitro-containing oxime compound.

[0866] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0867] As a photoradical polymerization initiator, oxime compounds with hydroxyl substituents bonded to the carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, and this content is included in this specification.

[0868] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group ArOX1 with an electron-withdrawing group introduced onto the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic ArOX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred for the ease of forming a film with excellent lightfastness, with benzoyl being even more preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio or amino are even more preferred, and alkoxy, alkylthio or amino are further preferred.

[0869] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and formula (OX2), with the compound represented by formula (OX2) being more preferred.

[0870]

[0871] In the formula, RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphine, aminomethyl, or aminosulfonyl; RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; RX3 to RX14 each independently represent a hydrogen atom or a substituent; wherein at least one of RX10 to RX14 is an electron-withdrawing group.

[0872] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13, and RX14 are preferably hydrogen atoms.

[0873] As a specific example of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 are cited, and this content is incorporated into this specification.

[0874] Examples of optimal oxime compounds include those with specific substituents as shown in Japanese Patent Application Publication No. 2007-269779 or those with thioaryl groups as shown in Japanese Patent Application Publication No. 2009-191061, and these are included in this specification.

[0875] From the perspective of exposure sensitivity, photoradical polymerization initiators are selected from those including trihalomethanes. Compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetylsphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl Compounds from the group consisting of diazole compounds and 3-aryl-substituted coumarin compounds are preferred.

[0876] A further preferred photoradical polymerization initiator is trihalomethyltri ... Compounds, α-aminoketone compounds, acetylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, ononium salt compounds, benzophenone compounds, acetophenone compounds, selected from compounds including trihalomethanes. It is further preferred to use at least one compound from the group consisting of compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds, and it is even more preferred to use metallocene compounds or oxime compounds.

[0877] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by cyclization of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; and benzyl derivatives such as benzyl dimethyl ketal. Additionally, compounds represented by formula (I) below can also be used.

[0878]

[0879] In formula (I), RI00 is an alkyl group with 1 to 20 carbon atoms, an alkyl group with 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbon atoms or a phenyl group, or an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group with 2 to 12 carbon atoms, an alkyl group with 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group with 1 to 4 carbon atoms, at least one of which is a phenyl or biphenyl group. RI01 is a group represented by formula (II) or a group that is the same as RI00. RI02 to RI04 are each independently an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms or a halogen atom.

[0880]

[0881] In the formula, RI05~RI07 are the same as RI02~RI04 in the above formula (I).

[0882] Furthermore, the photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, and this content is incorporated into this specification.

[0883] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and ( ) described in Japanese Patent Application Publication No. 2013-522445. G) Cmpd1-7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators as described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) as described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent No. 6469669, etc., and these contents are incorporated into this specification.

[0884] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention 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. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, the total amount within the above-mentioned range is preferred.

[0885] Furthermore, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0886] [Sensitizer]

[0887] The resin composition may include sensitizers. Sensitizers absorb specific active radiation to become electronically excited. These electronically excited sensitizers then come into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., thereby generating electron transfer, energy transfer, and heat generation. Consequently, the thermal free radical polymerization initiators and photofree radical polymerization initiators undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0888] As usable sensitizers, benzophenone-based, milchnerone-based, coumarin-based, pyrazole azo, aniline azo, triphenylmethane-based, anthraquinone-based, anthracene-based, anthraquinone-based, benzylene-based, oxacyanine-based, pyrazolotriazole azo, pyridone azo, anthocyanin-based, and phenanthrene-based sensitizers are all suitable. Series, pyrrolopyrazole azomethine series, Compounds such as phenolic cyanine, benzopyran, and indigo compounds.

[0889] Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, and 4,4'-bis(diethylamino)chalcone. Chalcone, p-dimethylaminophenylenepropyl dihydroindone, p-dimethylaminobenzyl dihydroindone, 2-(p-dimethylaminophenylbenzyl)-benzothiazole, 2-(p-dimethylaminophenylenevinyl)benzothiazole, 2-(p-dimethylaminophenylenevinyl)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethyl)acetone (aminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzo[] Zyrazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoaniline, N-methylacetamide, 3',4'-dimethylacetamide, etc.

[0890] Alternatively, other sensitizing pigments can be used.

[0891] For details regarding the sensitized pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated into this specification.

[0892] When the resin composition contains a sensitizer, the sensitizer content relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass. A single sensitizer may be used, or two or more may be used simultaneously.

[0893] [Chain transfer agent]

[0894] The resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 3rd edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithioaminocarbamate, and xanthate compounds having a thiocarbonyl sulfide group for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0895] Furthermore, the chain transfer agent may also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, and this content is incorporated into this specification.

[0896] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content is within the above-mentioned range.

[0897] <Thermal polymerization initiator>

[0898] It is also preferable that the resin composition of the present invention contains a thermal polymerization initiator.

[0899] In particular, by including a thermal polymerization initiator in the second resin composition, for example in the second pre-heating step or the second post-heating step described above, the polymerization of the polymerizable compound can be promoted.

[0900] As a thermal polymerization initiator, it can be selected according to the type of polymerizable compound, but thermal free radical polymerization initiators are preferred. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy and initiate or promote the polymerization reaction of polymerizable compounds.

[0901] Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization by heat, and can sometimes be added as thermal polymerization initiators.

[0902] Examples of known azo compounds and peroxide compounds can be cited as thermal polymerization initiators. Examples of azo compounds include azobisides. Azo compounds can be compounds containing a cyano group or compounds without a cyano group. Examples of peroxide compounds include ketone peroxides, peroxy acetals, hydroperoxides, dialkyl peroxides, diacyl peroxides, dicarbonates, and peroxide esters.

[0903] Commercially available products can also be used as thermal polymerization initiators, such as V-40, V-601, and VF-096 manufactured by FUJIFILM Wako Pure Chemical Corporation, and PERHEXYL O, PERHEXYL D, PERHEXYL I, PERHEXA 25O, PERHEXA 25Z, PERCUMYL D, PERCUMYL D-40, PERCUMYL D-40 MB, PERCUMYL H, PERCUMYL P, and PERCUMYL ND.

[0904] Furthermore, as a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited, and this content is incorporated into this specification.

[0905] The content of the thermal polymerization initiator in the resin composition (especially the second resin composition) is preferably 0.05% by mass or more and 10% by mass or less relative to the total solid content of the second resin composition, more preferably 0.1% by mass or more and 10% by mass or less, further preferably 0.1% by mass or more and 5% by mass or less, and especially preferably 0.5% by mass or more and 3% by mass or less.

[0906] The resin composition (especially the second resin composition) may contain only one thermal polymerization initiator, or it may contain two or more. When it contains two or more initiators, it is preferable that their total amount is within the range described above.

[0907] [Photoacid generator]

[0908] It is preferable that the resin composition of the present invention contains a photoacid generating agent.

[0909] A photoacid generator is a compound that produces at least one of Bristol acid and Lewis acid upon irradiation with light in the range of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, and more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator capable of producing acid upon photosensitization is preferred.

[0910] Examples of acids produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonic acid amides.

[0911] Examples of photoacid generators used in the resin composition of this invention include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfonic acid compounds, and onium salts.

[0912] From the perspective of sensitivity and storage stability, organohalogen compounds, oxime sulfonates, and onium salts are preferred; from the perspective of the mechanical properties of the formed film, oxime esters are preferred.

[0913] Examples of quinone diazide compounds include those obtained by attaching a sulfonate bond of quinone diazide to a monovalent or polyvalent hydroxyl group, those obtained by attaching a sulfonamide bond of quinone diazide to a monovalent or polyvalent amine group, and those obtained by attaching a sulfonate bond and / or a sulfonamide bond of quinone diazide to a polyhydroxy polyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinone diazide, but it is preferable that at least 40 moles of the total functional groups are substituted with quinone diazide. By containing such a quinone diazide compound, a resin composition capable of photosensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from a typical ultraviolet mercury lamp can be obtained.

[0914] Examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tributanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, and BisOCHP-Z. BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (These are product names, Honshu Chemical Industry) The products include, but are not limited to, BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc.

[0915] Examples of amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, etc., but are not limited to these.

[0916] Furthermore, examples of polyhydroxy polyamine compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited to these.

[0917] Among these, compounds containing phenolic compounds and esters with 4-naphthoquinone diazidesulfonyl groups are preferred as quinone diazide compounds. This allows for higher sensitivity and higher resolution to i-ray exposure.

[0918] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by weight, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. By setting the content of the quinone diazide compound within this range, the contrast between the exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is therefore preferable. Furthermore, sensitizers or the like can be added as needed.

[0919] It is preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound").

[0920] There are no particular restrictions on the presence of an oxime sulfonate group in oxime sulfonate compounds, but oxime sulfonate compounds represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) are preferred.

[0921]

[0922] In formula (OS-1), X3 represents an alkyl, alkoxy, or halogen atom. When multiple X3s are present, they may be the same or different. The alkyl and alkoxy atoms in X3 may have substituents. As the alkyl group in X3, a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in X3, a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in X3, a chlorine or fluorine atom is preferred.

[0923] In equation (OS-1), m3 represents an integer from 0 to 3, with 0 or 1 being preferred. When m3 is 2 or 3, the complex number of X3 can be the same or different.

[0924] In formula (OS-1), R34 represents an alkyl or aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an anthracene group that can be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloaryl group having 6 to 20 carbon atoms.

[0925] In formula (OS-1), m3 is 3, X3 is methyl, X3 is substituted at the ortho position, and R34 is preferably a straight-chain alkyl group with 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonormethylmethyl or p-tolyl.

[0926] As specific examples of oxime sulfonate compounds represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674 are examples, and such contents are incorporated into this specification.

[0927]

[0928] In formulas (OS-103) to (OS-105), Rs1 represents alkyl, aryl, or heteroaryl. Sometimes there are multiple Rs2 that independently represent hydrogen atoms, alkyl, aryl, or halogen atoms. Sometimes there are multiple Rs6 that independently represent halogen atoms, alkyl, alkoxy, sulfonic acid, aminosulfonyl, or alkoxysulfonyl. Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6.

[0929] In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbons), aryl group (preferably with 6 to 30 carbons), or heteroaryl group (preferably with 4 to 30 carbons) represented by Rs1 may have known substituents within the range that can achieve the effects of the present invention.

[0930] In formulas (OS-103) to (OS-105), Rs2 is preferably a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms), or an aryl group (preferably with 6 to 30 carbon atoms), with hydrogen or alkyl being more preferred. In compounds where two or more Rs2 atoms are present, it is preferred that one or two are alkyl, aryl, or halogen atoms, more preferred that one is alkyl, aryl, or halogen atom, and especially preferred that one is alkyl and the remainder are hydrogen atoms. The alkyl or aryl group represented by Rs2 may have known substituents within the range that allows the effects of the present invention to be obtained.

[0931] In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, with O being preferred. In formulas (OS-103) to (OS-105) above, a ring containing Xs as a member is a 5-member ring or a 6-member ring.

[0932] In equations (OS-103) to (OS-105), ns represents 1 or 2. When Xs is 0, ns is better if it is 1, and when Xs is S, ns is better if it is 2.

[0933] In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) represented by Rs6 may have substituents.

[0934] In equations (OS-103) to (OS-105), ms represents an integer from 0 to 6, an integer from 0 to 2 is preferred, 0 or 1 is even better, and 0 is the best.

[0935] Furthermore, the compound represented by the above formula (OS-103) is preferably represented by the compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is preferably represented by the compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is preferably represented by the compound represented by the following formula (OS-108) or formula (OS-109).

[0936]

[0937] In formulas (OS-106) to (OS-111), Rt1 represents alkyl, aryl, or heteroaryl; Rt7 represents hydrogen or bromine; Rt8 represents hydrogen, alkyl with 1 to 8 carbon atoms, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl; Rt9 represents hydrogen, halogen, methyl, or methoxy; and Rt2 represents hydrogen or methyl.

[0938] In formulas (OS-106) to (OS-111), Rt7 represents a hydrogen atom or a bromine atom, with hydrogen atom being preferred.

[0939] In formulas (OS-106) to (OS-111), Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. It is preferred that the alkyl group having 1 to 8 carbon atoms, the halogen atom, or the phenyl group has 1 to 8 carbon atoms, the alkyl group having 1 to 6 carbon atoms is even more preferred, and the methyl group is particularly preferred.

[0940] In formulas (OS-106) to (OS-111), Rt9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with hydrogen atom being preferred.

[0941] Rt2 represents a hydrogen atom or a methyl group, with hydrogen atom being preferred.

[0942] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be either one or a mixture.

[0943] As specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 are examples, and such contents are incorporated into this specification.

[0944] Other preferred forms of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

[0945]

[0946] In formula (OS-101) or formula (OS-102), Ru9 represents a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acetyl, aminomethyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. It is preferred that Ru9 is cyano or aryl, and it is further preferred that Ru9 is cyano, phenyl, or naphthyl.

[0947] In formula (OS-101) or formula (OS-102), Ru2a represents alkyl or aryl.

[0948] In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NRu5-, -CH2-, -CRu6H- or CRu6Ru7-, and Ru5 to Ru7 represent alkyl or aryl groups, respectively.

[0949] In formula (OS-101) or formula (OS-102), Ru1 to Ru4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amino group, a sulfonyl group, a cyano group, or an aryl group. Two of Ru1 to Ru4 can be bonded together to form a ring. In this case, the ring can undergo ring condensation to form a condensed ring together with the benzene ring. Preferably, Ru1 to Ru4 are hydrogen atoms, halogen atoms, or alkyl groups, and it is also preferred that at least two of Ru1 to Ru4 are bonded together to form an aryl group. Preferably, all of Ru1 to Ru4 are hydrogen atoms. The above-mentioned substituents may also have substituents.

[0950] The compound represented by formula (OS-101) is preferred over the compound represented by formula (OS-102).

[0951] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure of the oxime or benzothiazole ring (E, Z, etc.) can be either one of them or a mixture thereof.

[0952] As specific examples of compounds represented by formula (OS-101), compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674 are examples, and such contents are incorporated into this specification.

[0953] Among the above compounds, b-9, b-16, b-31, and b-33 are preferred.

[0954] [Chemical Formula 44]

[0955] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0956] Alternatively, the following compounds represented by the structural formulas can be cited as better examples.

[0957]

[0958] As organohalogenated compounds, examples include Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and MP Hutt's "Jurnal of Heterocyclic". The compounds described in Chemistry 1 (No. 3), (1970), etc., are included in this specification. In particular, compounds substituted with trihalomethyl groups can be cited. Azole compounds: S-triazole The compound is a preferred example.

[0959] More preferably, at least one mono, di, or trihalogenated substituted methyl group and s-trihalogenated methyl group can be cited. S-3 formed by ring bonding Derivatives, specifically, for example, 2,4,6-tris(monochloromethyl)-s-tris 2,4,6-Tris(dichloromethyl)-s-tris 2,4,6-Tris(trichloromethyl)-s-tris 2-Methyl-4,6-bis(trichloromethyl)-s-tri 2-n-propyl-4,6-bis(trichloromethyl)-s-tri 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tri 2-Phenylacetyl-4,6-bis(trichloromethyl)-s-tri 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-tri 2-Styryl-4,6-bis(trichloromethyl)-s-tri 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-tri 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-tri 2-(p-Tolyl)-4,6-bis(trichloromethyl)-s-tri 2-(4-naphthoxynaphthyl)-4,6-bis(trichloromethyl)-s-tri 2-Phenylenyl-4,6-bis(trichloromethyl)-s-tri 2-Benzylthio-4,6-bis(trichloromethyl)-s-tri 2,4,6-Tris(dibromomethyl)-s-tris 2,4,6-Tris(tribromomethyl)-s-tris 2-Methyl-4,6-bis(tribromomethyl)-s-tri 2-Methoxy-4,6-bis(tribromomethyl)-s-tri wait.

[0960] Examples of organoborate compounds include, for example, Japanese Patent Application Publication No. 62-143044, Japanese Patent Application Publication No. 62-150242, Japanese Patent Application Publication No. 9-188685, Japanese Patent Application Publication No. 9-188686, Japanese Patent Application Publication No. 9-188710, Japanese Patent Application Publication No. 2000-131837, Japanese Patent Application Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Publication No. 2002-116539, etc., and Kunz, Martin, “Rad Tech’98. Proceeding April”. The organoborates described in "Chicago" etc., Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and the organoboron-strontium complexes or organoboron-oxystrontium complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553, and the organoboron-strontium complexes described in Japanese Patent Application Publication Nos. 19-22, 1998, etc. The present specification includes, as specific examples, organoboron-phosphorus complexes described in Japanese Patent Application Publication No. 9-188710, organoboron-transition metal coordination complexes such as those in Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, and Japanese Patent Application Publication No. 7-292014, and such contents.

[0961] Examples of diazonium compounds include compounds described in Japanese Patent Application Publication No. 61-166544, Japanese Patent Application Publication No. 2001-132318, and diazonium compounds.

[0962] Examples of the aforementioned onium salt compounds include, for instance, the diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21, 423 (1980); the ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc.; the phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; the specifications of European Patent No. 104,143, U.S. Patent No. 339,049, and U.S. Patent No. 410,201; and Japanese Patent Application Publication Nos. 2-150848 and 2-296514. The described ferrous salts are found in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442; US Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827; and German Patent No. 2,904,626. The specifications of German Patent Nos. 3,604,580 and 3,604,581 contain strontium salts, selenium salts, arsenic salts, pyridinium salts, etc., as described in JVCrivello et al., Macromolecules, 10(6), 1307(1977), JVCrivello et al., J.Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), and arsenic salts, pyridinium salts, etc., as described in CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988). These contents are included in this specification.

[0963] As onium salts, examples of onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited.

[0964]

[0965] In formula (RI-I), Ar11 represents an aryl group having 1 to 6 substituents with 20 or fewer carbon atoms. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 2 to 12 carbon atoms, alkylamino groups with 1 to 12 carbon atoms of alkyl groups or arylamino groups with 6 to 20 carbon atoms of aryl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. Z11- represents a monovalent anion, which can be a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. From the perspective of stability, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferred. In formula (RI-II), Ar21 and Ar22 each independently represent aryl groups with 1 to 20 carbon atoms that may have 1 to 6 substituents. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms of alkyl groups, alkylamino or arylamino groups with 1 to 12 carbon atoms of alkyl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. Z21- represents a monovalent anion, which can be a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. Considering stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, or carboxylic acid ion are preferred. In formula (RI-III), R31, R32, and R33 each independently represent an aryl or alkyl, alkenyl, or alkynyl group with 1 to 6 substituents and 6 to 20 carbon atoms. Preferably, considering reactivity and stability, an aryl group is preferred. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamino or arylamino groups having 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms.Z31- represents a monovalent anion, which can be a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. Considering stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, or carboxylic acid ion are preferred.

[0966] Specific examples of preferred photoacid generators include the following.

[0967]

[0968]

[0969] [Chemical Formula 49]

[0970] [Chemical Formula 50]

[0971] In the above formula, Rf represents a perfluoroalkyl group.

[0972] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the resin composition, more preferably at 0.5 to 18% by mass, further preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass.

[0973] A photoacid generator can be used alone or in combination with multiple agents. When multiple agents are used in combination, the total amount is preferably within the range mentioned above.

[0974] Furthermore, it is better to use it in conjunction with a sensitizer in order to impart photosensitivity to the desired light source.

[0975] <Alkali-generating agents>

[0976] The resin composition of the present invention may include an alkali generating agent. The alkali generating agent is a compound capable of generating alkali through physical or chemical action. Preferred alkali generating agents for the resin composition of the present invention include thermal alkali generating agents and photo-alkali generating agents.

[0977] In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali-generating agent. By including a thermal alkali-generating agent in the resin composition, such as one that can promote the cyclization reaction of the precursor by heating, the mechanical properties or chemical resistance of the cured material are improved, for example, its performance as an interlayer insulating film for redistribution layers included in semiconductor packages becomes better.

[0978] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from a base-generating agent include secondary and tertiary amines.

[0979] There are no particular limitations on the alkali-generating agent of the present invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonic acid acetamide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, and acetoimine compounds.

[0980] Specific compounds that can be cited as nonionic base generating agents include those represented by formulas (B1), (B2), or (B3).

[0981]

[0982] In formulas (B1) and (B2), Rb1, Rb2, and Rb3 are independently an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Rb1 and Rb2 do not simultaneously constitute hydrogen atoms. Furthermore, Rb1, Rb2, and Rb3 do not possess a carboxyl group. Moreover, in this specification, a tertiary amine structure refers to a structure where all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to the case where the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0983] In formulas (B1) and (B2), it is preferred that at least one of Rb1, Rb2, and Rb3 contains a cyclic structure, and it is even more preferred that at least two of them contain a cyclic structure. The cyclic structure can be any of a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. It is preferred that the monocyclic ring is a 5-membered or 6-membered ring, with a 6-membered ring being more preferred. It is preferred that the monocyclic ring is a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0984] More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), alkenyl groups (preferably with 2-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), aryl groups (preferably with 6-22 carbon atoms, more preferably with 6-18 carbon atoms, and further preferably with 6-10 carbon atoms), or aralkyl groups (preferably with 7-25 carbon atoms, more preferably with 7-19 carbon atoms, and further preferably with 7-12 carbon atoms). These groups may have substituents within the range that enables the effects of the present invention. Rb1 and Rb2 may be bonded to each other to form a ring....

Claims

1. A method for manufacturing a permanent film, comprising: The step of forming a layer of the first resin composition on a substrate using the first resin composition to obtain a substrate having the first pattern; The steps of applying a second resin composition to a substrate having the aforementioned first pattern to form a second resin composition layer in at least one of the regions on and between the first pattern; and the steps of removing a portion of the second resin composition layer to form a second pattern in contact with the first pattern, wherein the aforementioned second resin composition includes a filler, and the filler included in the aforementioned second resin composition is at least one filler selected from the group consisting of silicon dioxide, quartz, glass, ceramics, fluoropolymers and liquid crystal polymers.

2. The method for manufacturing a permanent film as claimed in claim 1, wherein the area between the patterns in the composite pattern formed by the aforementioned first pattern and the aforementioned second pattern is narrower than the area between the patterns in the aforementioned first pattern.

3. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the filler included in the aforementioned second resin composition is at least one filler selected from the group consisting of hollow particles and porous particles.

4. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the dielectric loss tangent of the aforementioned filler is less than 0.

01.

5. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the aforementioned first resin composition is a negative photosensitive resin composition.

6. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the step of obtaining a substrate having the aforementioned first pattern is a step of selectively exposing the aforementioned first resin composition layer and then developing it by solvent development.

7. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the step of forming the aforementioned second pattern is a step of removing a portion of the aforementioned second resin composition layer by solvent development.

8. The method for manufacturing a permanent film as described in claim 1 or claim 2, further comprising, after the step of forming the aforementioned second resin composition layer and before the step of forming the aforementioned second pattern, a step of heating the aforementioned first pattern and the aforementioned second resin composition layer.

9. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the aforementioned second resin composition comprises a thermal polymerization initiator.

10. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the aforementioned second resin composition comprises a resin having a polymerizable group.

11. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the resin contained in the aforementioned first resin composition is a polyimide precursor or a polybenzoxazole precursor.

12. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the resin contained in the aforementioned second resin composition is a polyimide precursor or a polybenzoxazole precursor.

13. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the aforementioned second resin composition comprises a polymeric compound having an aromatic group as the polymeric compound.

14. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the obtained permanent film comprises polyimide or polybenzoxazole.

15. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the ratio of the coefficient of thermal expansion of the second pattern to that of the first pattern is 60% or less.

16. A method for manufacturing a permanent film as described in claim 1 or claim 2, wherein the aforementioned first pattern comprises at least one of a hole pattern and a groove pattern.

17. A method for manufacturing a laminate, comprising a method for manufacturing a permanent film as described in any one of claims 1 to 16.

18. A method of manufacturing an apparatus comprising a method of manufacturing a permanent film as described in any one of claims 1 to 16 or a method of manufacturing a laminate as described in claim 17.

19. A permanent film obtained by a method of manufacturing a permanent film according to any one of claims 1 to 16.

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