TW202244639A - Method for producing permanent film, method for producing multilayer body, and method for producing semiconductor device - Google Patents

Abstract

The present invention provides a method for producing a permanent film, the method comprising: a step for using a first resin composition to obtain a substrate having first patterns; a step for providing a second resin composition to form a coating film of the second resin composition on the first patterns and on a region between the first patterns; and a step for removing a portion of the coating film of the second resin composition and forming second patterns which are in contact with the first patterns. Compared to the inter-pattern region of the first patterns, the inter-pattern region of composite patterns composed of the first patterns and the second patterns is narrower. The present invention also provides: a method for producing a multilayer body, which includes the method for producing a permanent film; and a method for producing a semiconductor device, which includes the method for producing a permanent film or the method for producing a multilayer body.

Description

Manufacturing method of permanent film, manufacturing method of laminated body, and manufacturing method of semiconductor device

The present invention relates to a method for manufacturing a permanent film, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device.

In recent years, with the miniaturization of semiconductor elements and the like, various methods of forming fine patterns by lithography and the like in the manufacture of semiconductor elements have been studied. For example, Patent Document 1 describes a resin composition for forming a fine pattern, which includes a hydroxyl group-containing resin, a crosslinking component, and an alcohol solvent, and includes a compound having a specific structure as a crosslinking component. Patent Document 2 describes a coating forming agent for photoresist pattern miniaturization comprising (A) vinylpyrrolidone and (B) a water-soluble vinyl compound selected from components other than (A). An aqueous solution of a copolymer of at least one monomer is formed.

[Patent Document 1] International Publication No. 2008/105293 [Patent Document 2] Japanese Patent Laid-Open No. 2003-084460

When using a resin composition to form a patterned permanent film included in a device such as a semiconductor element, there is a need to miniaturize the shape of the obtained pattern (for example, to form a fine via hole pattern). The object of the present invention is to provide a method for producing a permanent film capable of forming a fine permanent film pattern, a method for producing a laminate including the method for producing the permanent film, and a method for producing the permanent film including the method for producing the above-mentioned laminate. The manufacturing method of the semiconductor device of the method.

Examples of typical embodiments of the present invention are shown below. <1> A method of manufacturing a permanent film, which includes: Using the first resin composition, forming a film of the first resin composition on the substrate to obtain a substrate with a first pattern; A step of applying a second resin composition on the substrate having the first pattern to form a film of the second resin composition on the first pattern and in a region between the first patterns; and A step of removing a part of the film of the second resin composition to form a second pattern in contact with the first pattern, A region between patterns in the composite pattern formed of the first pattern and the second pattern is narrower than a region between patterns in the first pattern. <2> The method for producing a cured film according to <1>, wherein the first resin composition is a negative radiation-sensitive resin composition. <3> The method for producing a permanent film as described in <1> or <2>, wherein the step of obtaining the base material having the first pattern is to selectively expose the first resin composition film, and then use a solvent to Developing A step of developing. <4> The method for producing a permanent film according to any one of <1> to <3>, wherein the step of forming the second pattern is to remove part of the film of the second resin composition by solvent development step. <5> The method for producing a permanent film according to any one of <1> to <4>, after the step of forming the film of the second resin composition and before the step of forming the second pattern, It further includes the step of heating the first pattern and the film of the second resin composition. <6> The method for producing a permanent film according to any one of <1> to <5>, wherein the second resin composition contains a thermal polymerization initiator. <7> The method for producing a permanent film according to any one of <1> to <6>, wherein the second resin composition contains a resin having a polymerizable group. <8> The method for producing a permanent film according to any one of <1> to <7>, wherein the second resin composition contains a compound having a polymerizable group and an oxene ring structure. <9> The method for producing a permanent film according to any one of <1> to <8>, wherein the resin contained in the first resin composition is a polyimide precursor or polybenzoxazole Precursor. <10> The method for producing a permanent film according to any one of <1> to <9>, wherein the resin contained in the second resin composition is a polyimide precursor or polybenzoxazole Precursor. <11> The method for producing a permanent film according to any one of <1> to <10>, wherein the obtained permanent film contains polyimide or polybenzoxazole. <12> The method for producing a permanent film according to any one of <1> to <11>, which further includes a heating step after the step of forming the second pattern. <13> The method for producing a permanent film according to any one of <1> to <12>, wherein the composite pattern has an elongation at break of 40% or more. <14> The method for producing a permanent film according to any one of <1> to <13>, wherein the first pattern includes at least one of a hole pattern and a groove pattern. <15> A method for producing a laminate comprising the method for producing the permanent film described in any one of <1> to <14>. <16> A method of manufacturing a semiconductor device comprising the method of manufacturing the permanent film described in any one of <1> to <14> or the method of manufacturing the laminate described in <15>. [Invention effect]

According to the present invention, there are provided a method for producing a permanent film capable of forming a fine permanent film pattern, a method for producing a laminate including the method for producing the above-mentioned permanent film, and a method for producing the above-mentioned permanent film or the method for producing the above-mentioned laminate. A method of manufacturing a semiconductor device.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range represented by "-" sign shows the range which includes the numerical value described before and after "-" as a lower limit and an upper limit, respectively. In this specification, the term "step" not only means 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. Regarding the notation of a group (atomic group) in this specification, the notation of substitution and unsubstituted notation includes both a group (atomic group) without a substituent and a group (atomic group) with a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, unless otherwise specifically stated, "exposure" includes not only exposure by light but also exposure by particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include bright-line spectra of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either, and "(meth)acrylic" means "acrylic" and "methacrylic". "Both or either of them, and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC), and are defined as polystyrene conversion values . In this specification, regarding weight average molecular weight (Mw) and number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) can be used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION above) were connected in series and used as a column to obtain it. Unless otherwise specified, the molecular weights are those measured using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, unless otherwise specified, the detection in the GPC measurement uses a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when "upper" or "lower" is described as "upper" or "lower" regarding the positional relationship of the layers constituting the laminate, other layers may exist above or below the reference layer among the plurality of layers concerned. That is, a third layer or element may be further interposed between the reference layer and the above-mentioned other layers, and the reference layer and the above-mentioned other layers do not need to be in contact. Also, unless otherwise specified, the direction in which layers are gradually stacked with respect to the substrate is referred to as "up", or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up". Up" and the opposite direction is called "down". Furthermore, the setting of the up and down directions is for the convenience of explaining this specification, and in an actual situation, the "up" direction in this specification may also be different from vertically upward. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more kinds of compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of preferable aspects is a more preferable aspect.

(Manufacturing method of permanent film) The manufacturing method of the permanent film of the present invention comprises: using a first resin composition, forming a film of the first resin composition on a substrate to obtain a substrate with a first pattern; a step of forming a film of the second resin composition on the first pattern and in a region between the first patterns by applying the second resin composition; and removing a part of the film of the second resin composition to form the first pattern In the step of contacting the second pattern, the area between the patterns in the composite pattern formed by the above-mentioned first pattern and the above-mentioned second pattern is narrower than the area between the patterns in the above-mentioned first pattern.

According to the manufacturing method of the permanent film of this invention, the pattern of a fine permanent film can be formed. The mechanism by which the above-mentioned effect can be obtained is not clear, but it is presumed as follows.

As described above, when using a resin composition to form a patterned permanent film included in a device such as a semiconductor element, there is a need to miniaturize the shape of the obtained pattern (for example, to form a fine hole pattern or a fine hole pattern). groove pattern, etc.) and other requirements. In the past, the pattern of the resin composition was formed by exposing and developing the resin composition in a pattern, or forming a photoresist pattern on the resin composition, and performing etching of the resin composition using the photoresist pattern as a mask. However, there is a limit to miniaturization of the pattern due to the characteristics of the material used, the limit of the exposure wavelength used for exposure, and the like. In the present invention, after forming the first pattern, a film of the second resin composition is formed on the first pattern, and then a part of the film of the second resin composition is removed to form the second pattern, whereby the first pattern and the second pattern are formed. The area between the patterns in the composite pattern formed by the 2 patterns is narrower than the area between the patterns in the first pattern. Here, the area between the patterns is narrow, that is, the distance between the patterns becomes small, so that fine patterns of the permanent film (for example, fine hole patterns, fine groove patterns, etc.) can be produced. Therefore, it is considered that a fine pattern with a smaller dimension between patterns can be formed than when only the first pattern is formed. That is, according to the present invention, for example, the limit size of a hole pattern, a trench pattern, and the like can be reduced.

In addition, in addition to the reduction in the size between the above-mentioned patterns, the thickness of the pattern itself can also be increased compared to the case where only the first pattern is formed. Therefore, it is also possible to increase the aspect ratio of the pattern. In addition, by making the first resin composition contain a resin having a polymerizable group, and making the second resin composition contain a component having a polymerizable group (resin having a polymerizable group, a polymerizable compound, etc.), the pattern can also be improved. reliability. In the above aspects, it is considered that the use of a resin composition containing the same resin as the first resin composition and the second resin composition also contributes to improvement in reliability. Here, the reliability of the pattern means that peeling between the base material and the pattern does not easily occur even after a long period of time.

Among them, in Patent Document 1 and Patent Document 2, there is no description about the case of producing a fine patterned permanent film.

An example of the manufacturing method of the permanent film of this invention is shown in FIG. 1. (a) of FIG. 1 shows an example of a base material having a first pattern 2 on a base material 1 . In (a) of FIG. 1 , the first pattern 2 is formed on the base material 1 , and an inter-pattern region 4 (a region where no pattern exists) is formed between the two first patterns. (b) of FIG. 1 shows an example of a state where a film of the second resin composition is formed on the first pattern and in the region between the first patterns. In (b) of FIG. 1 , the coating film 6 of the second resin composition is formed on the first pattern 2 and in the region 4 between the patterns. (c) of FIG. 1 shows a region 8 where the film of the second resin composition is removed when part of the film of the second resin composition shown in (b) of FIG. 1 is removed. The area outside the dotted line in (c) of FIG. 1 (the side opposite to the side where the film 6 of the second resin composition is in contact with the first pattern 2 ) is the area 8 to be removed. The removal method will be described later. (d) of FIG. 1 shows an example of a state where a part of the film of the second resin composition is removed. The region 8 in (c) of FIG. 1 is removed, and a composite pattern formed of the first pattern 2 and the second pattern 10 is formed in (d) of FIG. 1 . In (d) of FIG. 1 , the first pattern 2 and the second pattern 10 are described separately for convenience, but they may be integrally formed by covalent bonds or the like of components contained in each pattern. Wherein, the area 12 between the patterns of the composite pattern in (d) of FIG. 1 is narrower than the area 4 between the patterns in (a) of FIG. 1 . Thus, according to the manufacturing method of the permanent film of this invention, compared with the case where a pattern is formed only by a 1st pattern, the area|region between patterns can be narrowed. That is, a fine pattern can be formed. Each step included in the manufacturing method of the permanent film of the present invention will be described in detail below.

＜1st pattern forming step＞ The manufacturing method of the permanent film of the present invention includes the step of using the first resin composition, forming a film of the first resin composition on the substrate to obtain a substrate with a first pattern (also referred to as "the first pattern forming step") .). Details of the first resin composition will be described later. It is preferable that the first pattern forming step includes a first film forming step of applying the first resin composition to the substrate to form a film. In addition, the first pattern forming step includes the above-mentioned first film forming step, a first exposing step of selectively exposing the film formed in the first film forming step, and using a developer to expose the film exposed in the first exposing step The 1st image development process which develops and forms a pattern is more preferable. Among them, the step of obtaining the substrate having the first pattern is preferably a step of developing by solvent development after selectively exposing the first resin composition film. Solvent development means development using a developing solution containing an organic solvent described later as a developing solution. That is, the first resin composition film is preferably a photosensitive film used for exposure and development, and is preferably a photosensitive film used for exposure and development using a developing solution containing an organic solvent. Also, the first resin composition film may be a photosensitive film used in positive tone development or a photosensitive film used in negative tone development, but a photosensitive film used in negative tone development is more preferable. In the present invention, negative image development means image development in which non-exposed areas are removed by image development, and positive image image development means image image development in which exposed areas are removed by image development. Also, the first pattern forming step includes the first film forming step, the first exposure step, the first developing step, a first heating step of heating the pattern obtained by the first developing step, and At least one of the first post-development exposure steps in which the pattern obtained in the development step is exposed is particularly preferred.

Also, it is preferable that the first pattern includes at least one of a hole pattern (for example, a Via pattern) and a groove pattern. The hole pattern includes, for example, a hole pattern with a diameter of 0.5 to 100 μm, and a hole pattern with a diameter of 3 to 50 μm is preferable. Moreover, the shape of a hole is not specifically limited, For example, the hole pattern whose shape viewed from above is circular is mentioned. In the case of the above-mentioned circular shape, the diameter of the above-mentioned hole pattern represents the diameter of the above-mentioned circle, and when the above-mentioned shape is not circular, the diameter of the above-mentioned hole pattern represents the equivalent circle diameter of the shape of the hole pattern viewed from above (in In a shape with a certain area, the diameter of a circle with the same area as its area). The groove pattern includes, for example, a groove pattern with a groove width of 0.5 to 100 μm, and a groove pattern with a groove width of 3 to 50 μm is preferable. As a film thickness of a 1st pattern, 1-50 micrometers is preferable, 2-20 micrometers is more preferable, 3-15 micrometers is still more preferable.

[First film forming step] The method for producing a permanent film of the present invention preferably includes a first film forming step of applying a first resin composition to a substrate to form a film.

-Substrate- The type of substrate can be appropriately set according to the application, but it is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated Plating film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe (for example, any one of substrates formed of metals and substrates formed with metal layers such as electroplating or vapor deposition) ), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, mold substrate, electrode plate of plasma display panel (PDP), etc. In the present invention, especially semiconductor substrates are preferred, silicon substrates, Cu substrates and mold substrates are more preferred. In addition, layers such as an adhesive layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates. Moreover, the shape of a base material is not specifically limited, It may be circular or rectangular. As a size of a base material, if it is circular, it is 100-450 mm in diameter, for example, Preferably it is 200-450 mm. If it is a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Also, as the base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.

Also, when the first resin composition is applied to form a film on the surface of a resin layer (for example, a layer formed of a cured material) or the surface of a metal layer, the resin layer or the metal layer becomes the base material.

Coating is preferable as a method of applying the first resin composition to the substrate.

Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the film, more preferably a spin coating method, a slit coating method, a spray coating method, or an inkjet method, and from the viewpoint of the uniformity of the thickness of the film and the viewpoint of productivity, the spin coating method and The slit coating method is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration of the first resin composition or coating conditions according to the method. In addition, the coating method can also be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferred. For rectangular substrates, slit coating is preferred. A coating method, a spraying method, an inkjet method, etc. are preferable. In the case of a spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transferring the coating film formed in advance to a dummy support by the said application method to a base material can also be applied. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 or in paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used in the present invention. . Also, a step of removing excess film in the end portion of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR), back rinse (Back rinse), and the like. In addition, a pre-wetting step may also be used. In this pre-wetting step, before applying the first resin composition on the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the first resin is applied. Composition.

[1st drying step] The above-mentioned film may be subjected to a step of drying the formed film (layer) in order to remove the solvent after the first film forming step (layer forming step) (after applying the first resin composition to the substrate) (the first drying step). step). That is, the first pattern forming step may include a first drying step of drying the film formed in the first film forming step. Moreover, it is preferable to perform the said 1st drying process after a 1st film formation process, and before a 1st exposure process. The drying temperature of the film in the first drying step is preferably from 50°C to 150°C, more preferably from 70°C to 130°C, and still more preferably from 90°C to 110°C. Moreover, drying can also be performed by reducing pressure. As a drying time, 30 seconds - 20 minutes can be illustrated, 1 minute - 10 minutes are preferable, and 2 minutes - 7 minutes are more preferable.

[First Exposure Step] The method for producing a permanent film of the present invention may include a first exposure step of selectively exposing the film formed in the first film formation step. Selectively exposing means exposing a portion of the film. Moreover, by selectively exposing, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film. The amount of exposure is not particularly limited as long as the first resin composition can be exposed to light. For example, it is preferably 50 to 10,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ/cm ² for better.

The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

Regarding the exposure wavelength, if the relationship with the light source is explained, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3 ) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser Radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of radiation is 532nm and the third harmonic is 355nm and so on. Among them, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable. Thereby, a particularly high exposure sensitivity can be obtained. Also, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the film formed of the first resin composition, but examples include exposure using a photomask, exposure by laser direct imaging, etc. .

[The first post-exposure heating step] The said film can be used for the process (1st post-exposure heating process) of heating after exposure. That is, the manufacturing method of the permanent film of this invention may include the 1st post-exposure heating process which heats the film exposed by the 1st exposure process. The 1st post-exposure heating process can be performed after a 1st exposure process, and before a 1st image development process. The heating temperature in the first post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the heating step after the first exposure is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. Regarding the rate of temperature rise in the heating step after the first exposure, it is preferably 1 to 12°C/minute from the temperature at the beginning of heating to the maximum heating temperature, more preferably 2 to 10°C/minute, and 3 to 10°C/minute. Further better. In addition, the rate of temperature increase can be appropriately changed during the heating process. The heating means in the first post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, and the like can be used. Moreover, it is also preferable to carry out under the environment of low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.

[1st developing step] The said film after exposure can be used for the 1st image development process which develops using a developing solution, and forms a pattern. That is, the manufacturing method of the permanent film of this invention may include the 1st image development process which develops the film exposed by the 1st exposure process using a developing solution, and forms a pattern. One of the exposed portion and the non-exposed portion of the film is removed by performing development, and a pattern is formed. Here, the image development which removes the non-exposed part of a film by an image development process is called negative image development, and the image development which removes the exposed part of a film by an image image development process is called positive image image development.

-Developer- As a developing solution used in a 1st image development process, the developing solution containing alkaline aqueous solution or an organic solvent is mentioned.

When the developing solution is an alkaline aqueous solution, examples of alkaline compounds that can be included 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, methyl Diethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydrogen Tetraoctylammonium Oxide, Ethyltrimethylammonium Hydroxide, Butyltrimethylammonium Hydroxide, Methyltripentylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, Dimethylbis( 2-Hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. For example, in the case of using TMAH, the content of the basic compound in the developer is preferably 0.01 to 10% by mass in the total mass of the developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass. good.

When the developer contains an organic solvent, examples of the organic solvent preferably include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, etc. Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxy acetate base esters (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methyl oxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionates (example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy Alkyl propionate (e.g. methyl 2-alkoxy propionate, ethyl 2-alkoxy propionate, propyl 2-alkoxy propionate, etc. (for example, 2-methoxy propionate methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy - Methyl 2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2- Ethyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, 2-oxobutyl Ethyl acetate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Cellosolve-based 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 examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone Ketones, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, Desirable examples of arsonides include dimethyl aroxide, and preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, and diethylene glycol. Alcohol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide Wait.

When the developing solution contains an organic solvent, the organic solvent can be used 1 type or in mixture of 2 or more types. In the present invention, at least one developer selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfone, N-methyl-2-pyrrolidone, and cyclohexanone is particularly included. A developer is preferably a developer, more preferably a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfone, and most preferably a developer containing cyclopentanone.

When the developer contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass relative to the total mass of the developer. The above is excellent. Moreover, the said content may be 100 mass %.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

-How to supply the developer- The method of supplying the developing solution is not particularly limited as long as the desired pattern can be formed, and there are methods of immersing the substrate on which the film is formed in the developing solution, and supplying the developing solution to the film formed on the substrate using a nozzle. It can be used for spin-on-immersion development or continuous supply of developing solution. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, spray nozzles, and the like. From the viewpoint of the permeability of the developer, the removability of the non-image area, and the efficiency of production, the method of supplying the developer using a straight nozzle or the method of continuously supplying it using a spray nozzle is preferable. From the developer to the image From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, it is possible to rotate the substrate to remove the developer from the substrate after continuously supplying the developer using a straight nozzle, and then rotate the substrate to remove the developer from the substrate after continuously feeding it again using a straight nozzle after spin drying. The liquid step can also be repeated multiple times. Also, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the base material, a step of keeping the developer in a substantially static state on the base material, and using ultrasonic waves or the like to develop the developer on the base material can be adopted. The steps of liquid vibration and the steps combining them, etc.

As developing time, 10 seconds - 10 minutes are preferable, and 20 seconds - 5 minutes are more preferable. The temperature of the developing solution at the time of image development is not specifically defined, It can perform preferably at 10-45 degreeC, More preferably, it can carry out at 18-30 degreeC.

In an image development process, after the process using a developing solution, you may further perform the washing|cleaning (rinsing) of the pattern using a rinse solution. In addition, a method of supplying a rinse solution or the like before the developer in contact with the pattern is completely dried may be employed.

-washing fluid- When the developing solution is an alkaline aqueous solution, water, for example, can be used as a rinse solution. When the developing solution is a developing solution containing an organic solvent, as the rinse solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used. ).

As the organic solvent when the rinsing liquid contains an organic solvent, examples of esters include 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 alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxy acetate, etc.), alkyl 3-alkoxypropionates (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionate Alkyl esters (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)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl acetate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, 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 ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, cyclic terpenes such as limonene, and As alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol , methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethylsulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are still more preferable.

When the rinsing liquid contains an organic solvent, preferably 50% by mass or more of the rinsing liquid is an organic solvent, more preferably 70% by mass or more of an organic solvent, still more preferably 90% by mass or more of an organic solvent. In addition, 100% by mass of the rinsing liquid may be an organic solvent.

The rinse solution may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

-How to supply the rinse solution- The method of supplying the rinsing liquid is not particularly limited as long as the desired pattern can be formed, and there are methods of immersing the base material in the rinsing liquid, supplying the base material by flooding, and spraying the rinse liquid onto the base material. The method of supplying the rinsing liquid to the substrate, and the method of continuously supplying the rinsing liquid to the substrate through a mechanism such as a straight nozzle. From the viewpoint of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency of production, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is as follows: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, a method of supplying the rinse liquid using a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, spray nozzles, and the like. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned developed pattern through a straight nozzle, and more preferably a step of supplying a rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinse liquid in the rinse step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially static state on the base material, and a process of rinsing the base material by ultrasonic wave or the like can be adopted. The steps of liquid vibration and the steps combining them, etc.

The rinsing time is preferably from 10 seconds to 10 minutes, more preferably from 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly limited, but it can be preferably performed at 10°C to 45°C, more preferably at 18°C to 30°C.

[1st heating step] The pattern obtained by the 1st image development process (in the case of performing a rinsing process, the pattern after rinsing) can be used for the 1st heating process which heats the pattern obtained by the said image development. That is, the manufacturing method of the permanent film of this invention may include the 1st heating process which heats the pattern obtained by the 1st image development process. In addition, the method for producing a permanent film of the present invention may include a first heating step for a pattern obtained by another method without performing a developing step or a pattern obtained by a first film forming step. The film is heated. The heating temperature (maximum heating temperature) in the first heating step is preferably 50-200°C, more preferably 60-160°C, still more preferably 70-150°C, still more preferably 80-140°C, 90-120°C is particularly preferred.

The heating in the first heating step is preferably performed at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the highest heating temperature. The temperature increase rate is more preferably 2 to 10° C./minute, more preferably 3 to 10° C./minute. By setting the temperature increase rate at 1°C/min or more, excessive volatilization of acid or solvent can be prevented while ensuring productivity, and by setting the temperature increase rate at 12°C/min or less, the residual stress of the hardened product can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out the temperature increase rate from the temperature at the beginning of heating to the maximum heating temperature at a rate of 1 to 8°C/second, and more preferably 2 to 7°C/second. 3 to 6° C./second is more preferable.

The temperature at the start of heating is preferably from 20 to 120°C, more preferably from 20 to 100°C, and still more preferably from 20 to 80°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, the temperature at the start of heating is the temperature of the film (layer) after development (or after washing), for example, it is preferable to start heating from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the first resin composition. .

The heating time (heating time at the highest heating temperature) is preferably from 30 seconds to 120 minutes, more preferably from 60 seconds to 60 minutes, and still more preferably from 90 seconds to 30 minutes.

Heating can be done in stages. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5° C./min.

In terms of preventing the decomposition of a specific resin, the process is carried out in an environment with a low oxygen concentration by passing an inert gas such as nitrogen, helium, or argon in the first heating step and performing it under a reduced pressure. better. The oxygen concentration is preferably not more than 50 ppm (volume ratio), more preferably not more than 20 ppm (volume ratio). It does not specifically limit as a heating mechanism in a 1st heating process, For example, a hot plate, an infrared furnace, an electric oven, a hot-air oven, an infrared oven, etc. are mentioned.

[First post-development exposure step] Instead of or in addition to the above-mentioned first heating step, the pattern obtained by the first development step (in the case of a rinse step, the pattern after rinse) may also be used. In the first post-development exposure step of the pattern after the exposure development step. That is, the manufacturing method of the permanent film of this invention may include the 1st post-development exposure process which exposes the pattern obtained by the 1st development process. The manufacturing method of the permanent film of the present invention may include the first heating step and the first post-development exposure step, or may include only one of the first heating step and the first post-development exposure step. In the exposure step after the first development, for example, the reaction of cyclization of polyimide precursor and the like by exposure to photobase generator or the formation of acid-decomposable groups by exposure to photoacid generator can be promoted. reaction to withdrawal, etc. In the exposure step after the first development, at least a part of the pattern obtained in the first development step may be exposed, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the exposure step after the first development is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² in terms of exposure energy at a wavelength at which the photosensitive compound exhibits sensitivity. The first post-development exposure step can be performed, for example, using the light source used in the above-mentioned first exposure step, and it is preferable to use broadband light.

[Patterning process by etching] In addition, it is also preferable that the first pattern forming step is a step of including another film forming step after the above-mentioned first film forming step, and exposing and developing the film obtained by the other film forming step to pattern it. After etching, a step of forming a first pattern by performing an etching process using the above-mentioned pattern as a mask. As a method of patterning a film obtained by exposing, developing, etc. in another film forming step, the same method as the above-mentioned first exposing step and first developing step can be mentioned. Regarding the etching treatment, it can be performed with reference to a known method. Wherein, the above-mentioned etching may be dry etching or wet etching, but dry etching is preferred. Also, the pattern used as the mask may remain or be removed by the etching, but it is preferably removed.

<Second film formation step> The manufacturing method of the permanent film of the present invention comprises providing the second resin composition on the substrate having the above-mentioned first pattern, and forming a film of the second resin composition on the first pattern and in the region between the first patterns ( Hereinafter, it is also referred to as the "second resin composition film.") step (second film forming step). The second film forming step can be performed by the same method as the first film forming step except for the point of imparting the second resin composition on the base material having the first pattern. Also, the same drying step as the first drying step may be included as the second drying step. In the second film forming step, the film of the second resin composition can be formed, for example, on the entire surface of the substrate and the first pattern. In addition, the film of the second resin composition may be formed only on a part of the substrate and the first pattern. The thickness of the film of the second resin composition formed in the second film forming step (thickness of the film formed on the first pattern) is preferably 0.1 to 20 μm, more preferably 1 to 10 μm.

＜Second pattern forming step＞ The method for producing a permanent film of the present invention includes a step of removing a part of the film of the second resin composition to form a second pattern in contact with the first pattern. The second pattern only needs to be in contact with at least a part of the first pattern, but it is preferably formed so as to cover at least the side surface of the first pattern. In addition, the second pattern may be formed on all sides of the first pattern, or may be formed on only some of the plurality of sides existing on the first pattern. Moreover, it is also preferable to form so that it may cover the upper surface and the side surface of a 1st pattern from a viewpoint of raising an aspect ratio. When removing the film of the second resin composition, it is preferable to remove until a part of the substrate is exposed. That is, it is preferable that the area where the film of the second resin composition is removed includes at least an area where the first pattern does not exist. In this invention, the pattern formed from a 2nd pattern and a 1st pattern is also called a composite pattern.

The shape of the composite pattern is not particularly limited, and examples thereof include hole patterns (for example, Via patterns), groove patterns, and the like. The shape of the composite pattern is preferably the same as that of the above-mentioned first pattern except that the region between the patterns is narrowed. For example, in the present invention, in addition to narrowing the area between the patterns by performing the second pre-heating step and the developing step (if necessary, performing the second post-heating step), it is possible to form the same shape as the above-mentioned first pattern. Composite patterns of the same shape. For example, when the first pattern is a hole pattern, it is preferable that the composite pattern is a hole pattern whose diameter is smaller than that of the first pattern. Specifically, the diameter of the composite pattern as the hole pattern is preferably reduced by 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more, from the diameter of the first pattern as the hole pattern. When the composite pattern is a hole pattern, for example, a hole pattern with a diameter of 0.5 to 100 μm is mentioned, and a hole pattern with a diameter of 3 to 50 μm is preferable. The definition of the diameter of the hole pattern is as above. When the first pattern is a groove pattern, it is preferable that the composite pattern is a groove pattern whose groove width is smaller than that of the first pattern. Specifically, the groove width of the composite pattern as the groove pattern is preferably reduced by 0.1 μm or more, more preferably 0.3 μm or more, and 0.5 μm or more than the groove width of the first pattern as the groove pattern. Further better. When the composite pattern is a groove pattern, a groove pattern having a groove width of 0.5 to 100 μm is mentioned, and a groove pattern having a groove width of 3 to 50 μm is preferable.

[2nd developing step] It is preferable that the second pattern forming step includes a second developing step of using a developer solution to the film formed in the second film forming step (in the case of including the second pre-heating step, the second pre-heating step) The film after the step) is developed to form a pattern. However, the 2nd image development process can be performed by the method similar to a 1st image development process. Here, "the first pattern forming step", "the first resin composition" and the like in the first developing step are replaced with "the second pattern forming step", "the second resin composition" and the like, respectively. In addition, the developing time in the second developing step is preferably 1 minute to 20 minutes, more preferably 2 minutes to 10 minutes. Among them, the step of forming the second pattern is preferably a step of removing a part of the film of the second resin composition by solvent development. Solvent image development refers to image development using a developer solution containing an organic solvent as a developer solution.

＜The second pre-heating step＞ The method for producing a permanent film of the present invention may include heating the first pattern and the second resin composition film after the step of forming the film of the second resin composition and before the step of forming the second pattern. step (2nd pre-heating step). By the second pre-heating step, for example, the solubility of the second resin composition film in the developer in the second developing step can be adjusted, thereby facilitating the formation of a composite pattern. Heating in the second pre-heating step can be performed, for example, by the same method as in the above-mentioned first heating step. The heating temperature and heating time in the second pre-heating step may be determined according to the components contained in the second resin composition, the developer used in the second developing step, and the like. For example, as heating temperature, 80-180 degreeC is preferable, and 90-170 degreeC is more preferable.

＜The second post-heating step＞ The method for producing a permanent film of the present invention preferably further includes a heating step (second post-heating step) after the step of forming the above-mentioned second pattern. In particular, when at least one of the first resin composition and the second resin composition contains a polyimide precursor or a polybenzoxazole precursor, in the second post-heating step, the polyimide Resins such as precursors or polybenzoxazole precursors are cyclized to resins such as polyimide and polybenzoxazole. In addition, crosslinking of unreacted polymerizable groups in resins or compounds having polymerizable groups other than resins is also carried out. The heating temperature (maximum heating temperature) in the second post-heating step is preferably 50-350°C, more preferably 150-250°C, still more preferably 160-250°C, and most preferably 160-230°C .

In the second post-heating step, a step of accelerating the cyclization reaction of the polyimide precursor or the polybenzoxazole precursor in at least one of the first resin composition film and the second resin composition film by heating is better.

As for the heating in the second post-heating step, it is preferable to perform the heating at a rate of temperature increase of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10° C./minute, more preferably 3 to 10° C./minute. By setting the temperature increase rate at 1°C/min or more, excessive volatilization of acid or solvent can be prevented while ensuring productivity, and by setting the temperature increase rate at 12°C/min or less, the residual stress of the hardened product can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out the temperature increase rate from the temperature at the beginning of heating to the maximum heating temperature at a rate of 1 to 8°C/second, and more preferably 2 to 7°C/second. 3 to 6° C./second is more preferable.

The temperature at the start of heating is preferably from 20°C to 150°C, more preferably from 20°C to 130°C, and still more preferably from 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, the temperature at the start of heating is the temperature after developing the second resin composition film, for example, from 30 to 200°C lower than the boiling point of the solvent contained in the first resin composition or the second resin composition of the present invention. The temperature starts to warm up as better.

The heating time (heating time at the highest heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and still more preferably from 15 to 240 minutes.

In particular, when forming a multilayer laminate, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, still more preferably 100° C. or higher, and particularly preferably 120° C. or higher from the viewpoint of interlayer adhesion. good. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and still more preferably 240°C or lower.

Heating can be done in stages. As an example, the following steps can be performed: ramp from 25°C at 3°C/min to 120°C and hold at 120°C for 60 minutes, and ramp from 120°C at 2°C/min to 180°C and hold at 180°C for 120 minutes . In addition, as described in US Patent No. 9159547, it is also preferable to perform the treatment while irradiating ultraviolet rays. By such a pretreatment step, the properties of the membrane can be improved. The pretreatment step can be carried out within a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be a step of two or more stages. For example, the first stage pretreatment step may be performed in the range of 100-150°C, and the second stage pretreatment step may be performed in the range of 150-200°C. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5° C./min.

In order to prevent the decomposition of a specific resin, the second post-heating step is carried out in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, and performing it under a reduced pressure. is better. The oxygen concentration is preferably not more than 50 ppm (volume ratio), more preferably not more than 20 ppm (volume ratio). The heating mechanism in the second post-heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric oven, a hot-air oven, and an infrared oven.

[2nd post-exposure step] In addition, instead of the second post-heating step or in addition to the second post-heating step, a second post-exposure step may be included. The 2nd post-exposure process can be performed by the method similar to the said 1st post-development exposure process.

＜Metal layer formation process＞ The composite pattern obtained in the second pattern forming step (preferably the pattern used in the second post-heating step) can be used in the metal layer forming step of forming a metal layer on the composite pattern. That is to say, it is preferable that the manufacturing method of the permanent film of the present invention includes a metal layer forming step, and the metal layer forming step forms a metal layer on the obtained composite pattern (the pattern for the second post-heating step is preferably) .

The metal layer is not particularly limited, and existing metal types can be used, examples of which include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, copper and aluminum. Copper is more preferred, and copper is further preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining them can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are mentioned. As a preferable aspect of electroplating, electrolytic plating using copper sulfate or a copper cyanide plating solution is mentioned.

The thickness of the metal layer is preferably from 0.01 to 50 μm, more preferably from 1 to 10 μm, at the thickest portion.

＜Permanent film＞ The permanent film (that is, the composite pattern) obtained by the method for manufacturing the permanent film of the present invention preferably contains polyimide or polybenzoxazole. Wherein, at least one of the first pattern and the second pattern forming the permanent film only needs to contain polyimide or polybenzoxazole, but both the first pattern and the second pattern contain polyimide Or the aspect of polybenzoxazole is also one of the preferable aspects of the present invention. Among them, it is preferable that the permanent film obtained by the manufacturing method of the permanent film of the present invention contains polyimide. At this time, at least one of the first pattern and the second pattern forming the permanent film may contain polyimide, but an aspect in which both the first pattern and the second pattern contain polyimide is also One of the preferred aspects of the present invention.

Cyclic resins such as polyimide and polybenzoxazole are excellent in heat resistance, insulation, and the like, and thus can be applied to various applications by including such a cyclized resin in a permanent film. The use is not particularly limited, but if a semiconductor device for actual mounting is used as an example, utilization as an insulating film or a sealing material or a protective film can be mentioned. Moreover, it can also be used as a base film, a cover film, etc. of a flexible substrate.

Also, the elongation at break of the composite pattern obtained by the method for producing the permanent film of the present invention is preferably 40% or higher, more preferably 50% or higher, and still more preferably 60% or higher. About the said elongation at break, it can measure by the method shown in an Example.

[Second Pattern] The relative permittivity of the second resin composition under Condition 1 below is preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3.0 or less. The lower limit of the relative permittivity is not particularly limited, as long as it is 0 or more. The loss tangent of the second resin composition under Condition 1 below is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.002 or less. The lower limit of the above-mentioned loss tangent is not particularly limited, as long as it is 0 or more. Condition 1: Apply the composition to a thickness of 15 μm on a silicon wafer with an oxide film (SiO ₂ ) formed on the surface, dry at 100°C for 5 minutes, heat at 230°C for 180 minutes to form a cured film, and The relative permittivity and loss tangent of a single film of the composition prepared by immersing it in hydrogen fluoride were measured. The relative permittivity and loss tangent can be measured in accordance with JIS (Japanese Industrial Standards: Japanese Industrial Standards) R 1641 "Measurement method of microwave dielectric properties of precision ceramic substrates".

＜Use＞ Examples of the region to which the method for producing a permanent film of the present invention or the permanent film obtained by the method for producing a permanent film of the present invention can be applied include insulating films of electronic devices, interlayer insulating films for rewiring layers, and stress buffer films. . Other examples include sealing films, substrate materials (base film or cover film, interlayer insulating film for flexible printed circuit boards), or cases where patterns are formed by etching insulating films for actual mounting purposes as described above. For such uses, see, for example, Science & Technology Co., Ltd. "Highly Functional and Applied Technology of Polyimide", April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Basics and Applications of Polyimide Materials" "Development" issued in November 2011, Japan Polyimide/Aromatic Polymer Research Society/edited "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

In addition, the method for producing the permanent film of the present invention or the permanent film obtained by the method for producing the permanent film of the present invention can also be used for the manufacture of offset printing plates or screen plates, the use of etching shaped components, electronics, especially microelectronics In the manufacture of protective paint and dielectric layer, etc.

(Laminated body and method of manufacturing the laminated body) In the present invention, the laminate refers to a structure having a plurality of layers formed of the permanent film obtained by the method for producing the permanent film of the present invention. The laminate is a laminate including two or more layers formed of permanent films, and may be a laminate in which three or more layers are laminated. At least one of the two or more permanent film layers included in the laminate is a layer formed of a permanent film obtained by the method for producing a permanent film of the present invention, thereby suppressing shrinkage of the permanent film or From the viewpoint of the deformation of the permanent film accompanying the above-mentioned shrinkage, it is also preferable that all the layers formed of the permanent film included in the above-mentioned laminate are layers formed of the permanent film obtained by the method for producing the permanent film of the present invention. .

That is, the method for producing a laminate of the present invention preferably includes the method for producing the permanent film of the present invention, and more preferably includes repeating the steps of the method for producing the permanent film of the present invention a plurality of times.

The laminate of the present invention includes two or more layers of permanent films, and it is preferable to include a metal layer between any of the layers of permanent films. It is preferable to form the said metal layer by the said metal layer forming process. That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on a layer formed of the permanent film between the methods for producing the permanent film performed a plurality of times. A preferred aspect of the metal layer forming step is as described above. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers in which a first layer formed of a permanent film, a metal layer, and a second layer formed of a permanent film are sequentially laminated can be cited as a preferable one. . It is preferable that both the above-mentioned first layer formed of permanent film and the above-mentioned second layer formed of permanent film are layers formed of permanent film obtained by the method for producing the permanent film of the present invention. The resin composition used to form the above-mentioned first layer formed of permanent film and the resin composition used to form the above-mentioned second layer formed of permanent film may have the same composition or different compositions. thing. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

＜Stacking procedure＞ It is preferable that the method for producing a laminate of the present invention includes a lamination step. The lamination step is a series of (a) first pattern forming step, (b) second film forming step, (c) second pattern forming step on the surface of the composite pattern (permanent film) or metal layer in sequence step. If necessary, the above-mentioned second pre-heating step, second post-heating step, and the like may be further performed. In addition, the (d) metal layer forming step may be included after the (c) second pattern forming step (preferably, after the second post-heating step). It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the lamination step.

After the layering step, when the layering step is further performed, it may be after the above-mentioned exposure step, after the above-mentioned (c) second pattern forming step (or after the second post-heating step), or after the above-mentioned (d) metal layer forming step , and further carry out the surface activation treatment step. As the surface activation treatment, plasma treatment can be exemplified. The details of the surface activation treatment will be described later.

It is better to carry out the above lamination step 2 to 20 times, more preferably 2 to 9 times. For example, if resin layer (permanent film)/metal layer/resin layer (permanent film)/metal layer/resin layer (permanent film)/metal layer, set the resin layer (permanent film) to 2 or more and 20 or less The structure is preferable, and it is still more preferable to set it as the structure of 2 or more layers and 9 or less layers. The composition, shape, film thickness, and the like of each of the above-mentioned layers may be the same or different.

In the present invention, an aspect in which the permanent film is formed so as to further cover the metal layer after the metal layer is provided by the method for producing the permanent film of the present invention described above is preferable. Specifically, an aspect in which (a) the first pattern forming step, (b) the second film forming step, (c) the second pattern forming step, and (d) the metal layer forming step are repeated in order is mentioned. By alternately performing the lamination step of the permanent film obtained by the permanent film manufacturing method of the present invention and the metal layer forming step, the permanent film and the metal layer obtained by the permanent film manufacturing method of the present invention can be alternately laminated.

(Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer and the permanent film to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but it is also possible to perform surface activation treatment on the permanent film after the second pattern formation step of (c) above (preferably, after the second post-heating step). After the step, a metal layer forming step is performed. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the permanent film, or may be performed on at least a part of both the metal layer and the permanent film. It is preferable to perform a surface activation treatment on at least a part of the metal layer, and it is more preferred to perform a surface activation treatment on a part or all of a region where a permanent film is formed on the surface of the metal layer. In this way, by surface-activating the surface of the metal layer, it is possible to improve the adhesiveness with the permanent film provided on the surface. Moreover, it is also preferable to surface-activate a part or all of the permanent film. In this way, by surface-activating the surface of the permanent film, the adhesiveness with the metal layer and the permanent film provided on the surface-activated surface can be improved. In particular, when the permanent film is hardened, such as when performing negative tone development, it is less likely to be damaged by surface treatment, and it is easy to improve the adhesiveness. As the surface activation treatment, specifically, plasma treatment, corona discharge treatment, etc. Etching treatment of CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, dipping in hydrochloric acid aqueous solution to remove oxide film, dipping in Immersion treatment in an organic surface treatment agent containing a compound having at least one amine group and a thiol group, mechanical roughening treatment using a brush, plasma treatment, especially oxygen plasma treatment using oxygen as a raw material gas Treatment is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m ² , more preferably 1000-100,000 J/m ² , and most preferably 10,000-50,000 J/m ² .

(Manufacturing method of semiconductor device) The present invention also discloses a method of manufacturing a semiconductor device including the method of manufacturing the permanent film of the present invention or the method of manufacturing a laminate of the present invention. As a specific example of a semiconductor device using the permanent film obtained by the method for producing a permanent film of the present invention for forming an interlayer insulating film for a rewiring layer, refer to paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in Figure 1, and these contents are incorporated into this specification.

(1st resin composition and 2nd resin composition) Hereinafter, the components contained in the resin composition of the present invention will be described in detail. The first resin composition and the second resin composition may be the same composition or may have different compositions.

It is preferable that the first resin composition is a negative radiation-sensitive resin composition. The negative radiation-sensitive resin composition is a composition used for forming a negative photosensitive film. Among them, the first resin composition is preferably a composition comprising resin and at least one of a photopolymerization initiator and a photoacid generator, more preferably a composition comprising a resin and a photopolymerization initiator, and a composition comprising a resin, a photopolymerization The resin of the initiator and the polymerizable compound is further preferable. Also, it is preferable that the resin contained in the first resin composition is a polyimide precursor or a polybenzoxazole precursor. These components will be described later.

It is preferable that the 2nd resin composition is a thermosetting resin composition. Moreover, it is preferable that the 2nd resin composition contains a thermal polymerization initiator. It is preferable that the 2nd resin composition contains the resin which has a polymeric group as resin. Among them, it is preferable that the above-mentioned polymerizable group is a group capable of forming a polymer with the resin or polymerizable compound contained in the first resin composition. For example, when the first resin composition contains a radical polymerizable compound, it is preferable that the second resin composition contains a resin having a radical polymerizable group as the resin. Also, it is preferable that the resin contained in the second resin composition is a polyimide precursor or a polybenzoxazole precursor. Furthermore, from the viewpoint of the adhesiveness between the first pattern and the second pattern in the composite pattern, it is also preferable that the resin contained in the first resin composition and the resin contained in the second resin composition be the same resin. . For example, an aspect in which both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors can be mentioned. It is considered 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. These components will be described later.

Hereinafter, the components contained in the first resin composition and the second resin composition will be described in detail. In the following description, when simply saying "resin composition", it means both a 1st resin composition and a 2nd resin composition.

The resin composition of the present invention contains resin. Examples of the resin include the following cyclized resins, their precursors (specific resins), and other resins.

＜Specific resin＞ The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. The cyclization resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain means the relatively longest bonded chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like. The precursor of cyclized resin refers to the resin that becomes cyclized resin due to the change of chemical structure caused by external stimuli. It is more preferable to form a ring structure to become a cyclized resin. Examples of the precursor of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is to say, the resin composition of the present invention comprises polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide and polyamideimide At least one resin (specific resin) in the group of imine precursors is preferable as the specific resin. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. In the case where the specific resin has a radical polymerizable group, the resin composition of the present invention preferably includes the radical polymerization initiator described below, and more preferably includes the radical polymerization initiator described below and the radical crosslinking agent described below. . Furthermore, a sensitizer mentioned later can be included as needed. For example, a negative photosensitive film is formed from the resin composition of the present invention. In addition, the specific resin may have a polarity conversion group such as an acid decomposable group. When the specific resin has an acid-decomposable group, it is preferable that the resin composition of the present invention contains a photoacid generator described later. For example, a chemically amplified positive photosensitive film or a negative photosensitive film is formed from the resin composition of the present invention.

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but preferably include a repeating unit represented by the following formula (2). [chemical formula 1]

In formula (2), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent hydrogen Atom or monovalent organic group.

A ¹ and A ² in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A cycloaliphatic group having 3 to 20 carbons, an aromatic group having 3 to 20 carbons, or a combination thereof are preferred, and a group including an aromatic group having 6 to 20 carbons is more preferred. The above linear or branched aliphatic groups may be substituted by hydrocarbon groups containing heteroatoms in the chain, and the above cyclic aliphatic groups and aromatic groups may be substituted by ring-membered hydrocarbon groups containing heteroatom groups. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and groups represented by -Ar-L-Ar- are particularly preferable. Wherein, Ar is independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbons including a single bond or which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- or a combination of two or more of the above. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Diamine may use only 1 type, and may use 2 or more types. Specifically, it includes a straight chain or branched aliphatic group with 2 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 3 to 20 carbons, or a combination thereof The diamine is preferred, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. The above linear or branched aliphatic groups may be substituted by hydrocarbon groups containing heteroatoms in the chain, and the above cyclic aliphatic groups and aromatic groups may be substituted by ring-membered hydrocarbon groups containing heteroatom groups. Examples of the group containing an aromatic group include the following.

式中，A表示單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等組合中之基團為較佳，選自單鍵或可以經氟原子取代的碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-中之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [chemical formula 2]

In the formula, A represents a single bond or a divalent linking group, selected from a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S- , -SO ₂ -, -NHCO- or groups in these combinations are preferred, selected from single bonds or alkylene groups with 1 to 3 carbons that may be substituted by fluorine atoms, -O-, -C (= O)-, -S- or -SO ₂ - are more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C( CH ₃ ) ₂ - is further preferred. In the formula, * represents a bonding site with other structures.

As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine Cyclohexane 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'-di Methylcyclohexylmethane and isophorone diamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylene or 3,3-diaminodiphenylene, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4 ,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-amine phenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis( 3-amino-4-hydroxyphenyl)pyridine, bis(4-amino-3-hydroxyphenyl)pyridine, 4,4'-diamino-terphenyl, 4,4'-bis(4-amine phenyloxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-(2 -aminophenoxy)phenyl]pyridine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl Base-4,4'-diaminodiphenylphenyl, 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'-diamine Diphenylmethane, 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'-di Aminobiphenyl, 9,9'-bis(4-amino Phenyl) terrene, 4,4'-dimethyl-3,3'-diaminodiphenylene, 3,3',5,5'-tetramethyl-4,4'-diaminodi Phenylmethane, 2,4-Diaminocumene and 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, Acetylguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octyl Methylpentasiloxane, 2,7-diaminostilbene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, diaminobenzylaniline, Esters of aminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl) base) 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(trifluoro Methyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy base) diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2 , at least 1 of 2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl A diamine.

Moreover, the diamines (DA-1)-(DA-18) described in paragraph 0030-0031 of International Publication No. 2017/038598 are also preferable.

Moreover, the diamine which has two or more alkylene glycol units as described in paragraph 0032-0034 of International Publication No. 2017/038598 on a main chain can also be used preferably.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Among them, Ar is independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- Or a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價的有機基，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式4]

式（61）中，R ⁵⁸及R ⁵⁹分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為提供式（51）或式（61）的結構之二胺，可以舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。 Also, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 3]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents a bonding site with a nitrogen atom in formula (2). Examples of the monovalent organic groups of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), 1 to 6) fluorinated alkyl groups, etc. [chemical formula 4]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represent a bonding site with a nitrogen atom in formula (2). Examples of diamines providing the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

Also, R ¹¹¹ preferably includes a polycyclic aromatic ring structure. In particular, when the second resin composition includes a resin having a repeating unit represented by formula (2), R ¹¹¹ preferably includes a polycyclic aromatic ring structure. According to such an aspect, the relative permittivity of the permanent film can be lowered, thereby suppressing an increase in the resistance of the wiring, suppressing a decrease in the resistance of the permanent film, and the like in some cases. Examples of polycyclic aromatic ring structures include biphenyl structures, polyphenyl structures such as terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fenene ring structures, and acenaphthene ring structures. However, it is not limited to this. Among them, it is preferable that R ¹¹¹ contains at least one of a polyphenyl structure or a fenene ring structure.

式（5）中，R ¹¹²為單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-以及該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及-SO ₂-中之基團為更佳，選自包括-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-之群組中的2價的基團為進一步較佳。 R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [chemical formula 5]

In formula (5), R ¹¹² is a single bond or a divalent linking group selected from a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S- , -SO ₂ - and -NHCO- and groups in these combinations are preferred, selected from single bonds, alkylene groups with 1 to 3 carbons that may be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO ₂ - are more preferred, selected from the group including -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, A divalent group in the group of -S- and -SO ₂ - is more preferable.

Also, R ¹¹⁵ preferably includes a polycyclic aromatic ring structure. In particular, when the second resin composition includes a resin having a repeating unit represented by formula (2), R ¹¹⁵ preferably includes a polycyclic aromatic ring structure. According to such an aspect, the relative permittivity of the permanent film can be lowered, thereby suppressing an increase in the resistance of the wiring, suppressing a decrease in the resistance of the permanent film, and the like in some cases. Examples of polycyclic aromatic ring structures include biphenyl structures, polyphenyl structures such as terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fenene ring structures, and acenaphthene ring structures. However, it is not limited to this. Among them, it is preferable that R ¹¹⁵ contains at least one of a polyphenyl structure or a fenene ring structure.

式（O）中，R ¹¹⁵表示4價的有機基。R ¹¹⁵的較佳範圍與式（2）中之R ¹¹⁵的含義相同，較佳範圍亦相同。 About ^R115 , the tetracarboxylic-acid residue which remains after removing an anhydride group from tetracarboxylic dianhydride specifically, etc. are mentioned. As a structure corresponding to ^R115 , the polyimide precursor may contain only one kind of tetracarboxylic dianhydride residue, and may contain two or more kinds. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [chemical formula 6]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as the meaning of R ¹¹⁵ in the formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide 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' -Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and the alkyl groups having 1 to 6 carbons and alkoxy derivatives having 1 to 6 carbons.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. 2017/038598 can also be mentioned as a preferable example.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may also have an OH group. More specifically, R ¹¹¹ includes a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to contain a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Also, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoyl group. Azolyl, blocked isocyanate, amine. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. As the group having an ethylenically unsaturated bond, vinyl, allyl, isoallyl, 2-methallyl, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[chemical formula 7]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group, or a polyalkylene group. Preferred examples of ^R201 can include alkane groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, etc. Base, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH)CH ₂ -, polyalkylene, ethylidene, propylene and other alkylene, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, and polyalkyleneoxy are more preferred, and alkylene or polyalkylene such as ethylene and propylene are still more preferred. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different. In the case where the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Arrangements with patterns such as alternating patterns are also possible. The carbon number of the above alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, the number of the alkyleneoxy groups contained in a polyalkyleneoxy group (the number of repetitions of a polyalkyleneoxy group) is 2-20 preferably, 2-10 are more preferable, 2-6 are still more preferable. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a plurality of ethyleneoxy groups and a plurality of A group obtained by bonding two propoxyl groups is preferred, polyethyleneoxy or polypropoxyl is more preferred, and polyethyleneoxy is further preferred. In the group obtained by bonding a plurality of ethyleneoxy groups with a plurality of propyleneoxy groups, the ethyleneoxy groups and propyleneoxy groups can be arranged randomly, or arranged in blocks, or arranged alternately, etc. Patterned. The ethyleneoxy groups in these groups repeat several preferred aspects as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond includes N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity switching group such as an acid decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but the acetal group, ketal group, silyl group, and silyl ether A group, a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal group is more preferable from a viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl group, trimethylsilyl group, tertiary butoxycarbonylmethyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuryl group is preferable.

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Also, in order to improve the adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine include those in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used.

式（2-A）中，A ¹及A ²表示氧原子，R ¹¹¹及R ¹¹²分別獨立地表示2價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基，R ¹¹³及R ¹¹⁴中的至少一者為包含聚合性基之基團，兩者為包含聚合性基之基團為較佳。 The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain the repeating unit represented by the formula (2-A), the width of the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 8]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ independently have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Moreover, the structural isomer of the repeating unit represented by formula (2) may also be contained. It goes without saying that the polyimide precursor may contain other types of repeating units other than the repeating unit of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, an aspect in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units is mentioned. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyimide precursor except the terminal may also be the repeating unit represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000, even more preferably from 15,000 to 40,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 2,000-40,000, More preferably, it is 3,000-30,000, More preferably, it is 4,000-20,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and still more preferably 2.0 or higher. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly defined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. In the present specification, the degree of dispersion of molecular weight is a value calculated from weight average molecular weight/number average molecular weight. Also, when the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above plural polyimide precursors as one resin are within the above ranges.

〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developing solution mainly composed of an organic solvent. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23° C. with respect to 100 g of a 2.38% by mass tetramethylammonium aqueous solution. From the viewpoint of pattern formation, 0.5 g is dissolved. The above polyimides are preferred, and it is further preferred to dissolve 1.0 g or more of the polyimides. The upper limit of the above-mentioned dissolved amount is not particularly limited, but is preferably 100 g or less. Furthermore, from the viewpoint of film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In the present specification, the "main chain" means the relatively longest bonded chain among the molecules of the polymer compound constituting the resin, and the "side chain" means other bonded chains.

-Fluorine atom- It is also preferable that polyimide has a fluorine atom from the viewpoint of the film strength of the obtained organic film. Fluorine atoms, for example, contained in R ¹³² in the repeating unit represented by the following formula (4) or R ¹³¹ in the repeating unit represented by the following formula (4) are preferably contained in the following formula ( 4) R ¹³² in the repeating unit represented by or R ¹³¹ in the repeating unit represented by formula (4) described later is more preferable. The amount of fluorine atoms is preferably at least 5% by mass and preferably at most 20% by mass relative to the total mass of the polyimide.

-Silicon atom- It is also preferable that the polyimide has a silicon atom from the viewpoint of the film strength of the obtained organic film. For example, the silicon atom contained in the repeating unit represented by the following formula (4) is preferably contained in R ¹³¹ , which is included in the repeating unit represented by the following formula (4) as the structure of the organic modified (poly)siloxane described below R ¹³¹ is the best. In addition, the above-mentioned silicon atom or the above-mentioned organically modified (poly)siloxane structure may also be included in the side chain of polyimide, but it is preferably included in the main chain of polyimide. The amount of silicon atoms is preferably at least 1% by mass, more preferably at most 20% by mass, based on the total mass of the polyimide.

-Ethylenically unsaturated bond- It is preferable that polyimide has an ethylenically unsaturated bond from the viewpoint of the film strength of the obtained organic film. Polyimide may have an ethylenically unsaturated bond at a main chain terminal or may have an ethylenically unsaturated bond at a side chain, but preferably has an ethylenically unsaturated bond at a side chain. It is preferable that the said ethylenically unsaturated bond has radical polymerizability. It is preferable that an ethylenically unsaturated bond is contained in R ¹³² in the repeating unit represented by the following formula (4) or R ¹³¹ in the repeating unit represented by the following formula (4), as a group having an ethylenically unsaturated bond It is more preferable to include R ¹³² in the repeating unit represented by the following formula (4) or R ¹³¹ in the repeating unit represented by the following formula (4). Among these, it is preferable that an ethylenically unsaturated bond is contained in R ¹³¹ in the repeating unit represented by the following formula (4), and it is contained in the following formula (4) as a group having an ethylenically unsaturated bond. ^R131 in the repeating unit represented is more preferred. Examples of groups having ethylenically unsaturated bonds include groups having vinyl groups that are directly bonded to aromatic rings and may be substituted, such as vinyl, allyl, and vinylphenyl, and (meth)acryl groups. group, (meth)acryloyloxy group, a group represented by the following formula (IV), etc.

[chemical formula 9]

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

In formula (IV), R ²¹ represents an alkylene group with 2 to 12 carbons, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH- , a (poly)alkyleneoxy group with 2 to 30 carbon atoms (the carbon number of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the number of repetitions is 1 to 12 is Preferably, 1 to 6 are more preferred, and 1 to 3 are particularly preferred) or a combination of two or more of these. In addition, as the above-mentioned alkylene group having 2 to 12 carbon atoms, any one of straight-chain, branched-chain, cyclic, or a combination thereof may be used. As the above-mentioned alkylene group having 2 to 12 carbons, an alkylene group having 2 to 8 carbons is preferable, and an alkylene group having 2 to 4 carbons is more preferable.

式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等中的2個以上鍵結而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（IV）中的R ²¹所鍵結之氧原子的鍵結部位。 式（R1）～（R3）中，L中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣與上述的R ²¹中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 式（R1）中，X為氧原子為較佳。 式（R1）～（R3）中，*與式（IV）中的*的含義相同，較佳態樣亦相同。 式（R1）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有異氰酸酯基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸酯基乙酯等）進行反應而獲得。 式（R2）所表示之結構例如藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥乙酯等）進行反應而獲得。 式（R3）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸縮水甘油酯等）進行反應而獲得。 Among them, R ²¹ is preferably a group represented by any one of the following formulas (R1) to formula (R3), more preferably a group represented by formula (R1). [chemical formula 10]

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbons, a (poly)alkyleneoxy group having 2 to 30 carbons, or a combination of two or more of these. X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, ● represents a bonding site with an oxygen atom bonded to R ²¹ in formula (IV). In the formulas (R1) to (R3), the preferred aspect of the alkylene group with 2 to 12 carbons or the (poly)alkoxyl group with 2 to 30 carbons in L is the same as the carbon number in the above ^R21 Preferred aspects of the alkylene group of 2 to 12 or the (poly)alkyleneoxy group of 2 to 30 carbon atoms are the same. In the formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same. The structure represented by the formula (R1) is prepared, for example, by making a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.) obtained by the reaction. The structure represented by the formula (R2) is obtained, for example, by reacting polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) is obtained by, for example, reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) And get.

In formula (IV), * represents a bonding site with other structures, and the bonding site with the main chain of polyimide is preferable.

The amount of ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol/g, more preferably 0.0005 to 0.05 mol/g, based on the total mass of the polyimide.

-Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of polymerizable groups other than groups having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Wait. A polymerizable group other than a group having an ethylenically unsaturated bond is preferably contained in, for example, R ¹³¹ in a repeating unit represented by formula (4) described later. The amount of polymerizable groups other than groups having an ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g, based on the total mass of the polyimide.

-Polarity conversion group- The polyimide may have a polarity conversion group, such as an acid-decomposable group. The acid-decomposable groups in the polyimide are the same as the acid-decomposable groups described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred aspects are also the same. The polarity switching group is included in, for example, R ¹³¹ , R ¹³² , the terminal of polyimide, etc. in the repeating unit represented by the formula (4) described later.

-acid value- In the case of using polyimide for alkali development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more for further improvement. Moreover, the above-mentioned acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less. Also, when polyimide is used for development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of polyimide is 1 to 35 mgKOH/g. Preferably, 2-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is still more preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acidic group contained in polyimide, the acidic group with pKa 0-10 is preferable, and the acidic group of 3-8 is more preferable from a viewpoint of both storage stability and developability. pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka in consideration of the dissociation reaction of releasing hydrogen ions from the acid. In this specification, pKa is a calculated value based on ACD/ChemSketch (registered trademark) unless otherwise specified. Also, the values disclosed in "Revised 5th Edition: Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan can be referred to. Alternatively, when the acid group is a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such acid groups, polyimide preferably contains at least one selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

-Phenolic hydroxyl group- It is preferable that polyimide has a phenolic hydroxyl group from a viewpoint of making the developing speed by alkali developing solution suitable. Polyimide may have a phenolic hydroxyl group at a main chain terminal, or may have a phenolic hydroxyl group on a side chain. The phenolic hydroxyl group is preferably included in, for example, R ¹³² in the repeating unit represented by formula (4) described below or R ¹³¹ in the repeating unit represented by formula (4) described below. The amount of phenolic hydroxyl groups is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g, based on the total mass of the polyimide.

式（4）中，R ¹³¹表示2價的有機基，R ¹³²表示4價的有機基。 在具有聚合性基之情況下，聚合性基可以位於R ¹³¹及R ¹³²中的至少一者上，如下述式（4-1）或式（4-2）所示，亦可以位於聚醯亞胺的末端。 式（4-1） [化學式12]

式（4-1）中，R ¹³³為聚合性基，其他基團與式（4）的含義相同。 式（4-2） [化學式13]

R ¹³⁴及R ¹³⁵中的至少一者為聚合性基，在不是聚合性基之情況下為有機基，其他基團與式（4）的含義相同。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4). [chemical formula 11]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. In the case of having a polymerizable group, the polymerizable group can be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or it can be located on polyamide amine end. Formula (4-1) [Chemical Formula 12]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meanings as in formula (4). Formula (4-2) [Chemical Formula 13]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, or an organic group when it is not a polymerizable group, and the other groups have the same meaning as in formula (4).

Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, or the crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond. R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include the same ones as R ¹¹¹ in the formula (2), and the preferred range is also the same. In addition, as R ¹³¹ , diamine residue remaining after removing the amine group of diamine can be mentioned. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. As a specific example, an example of R ¹¹¹ in the formula (2) of the polyimide precursor can be given.

From the viewpoint of more effectively suppressing warpage during calcination, R ¹³¹ is preferably a diamine residue having at least 2 alkylene glycol units in the main chain. More preferably, it is a diamine residue containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and it is further preferably a diamine residue that does not contain an aromatic ring. base.

Examples of diamines containing a total of two or more ethylene glycol chains, propylene glycol chains, or both 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 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-amine ylpropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine etc., but not limited thereto.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same ones as R ¹¹⁵ in the formula (2), and the preferred range is also the same. For example, four linkages of a tetravalent organic group exemplified as R ¹¹⁵ are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

Moreover, ^R132 can mention the tetracarboxylic acid residue which remained after removing an anhydride group from tetracarboxylic dianhydride, etc. As a specific example, an example of R ¹¹⁵ in the formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, examples of R ¹³¹ include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1)～( DA-18) As a preferable example, as ^R132 , the said (DAA-1)-(DAA-5) can be mentioned as a more preferable example.

Moreover, it is also preferable that polyimide has a fluorine atom in a structure. The content of fluorine atoms in the polyimide is preferably at least 10% by mass, and more preferably at most 20% by mass.

Also, in order to improve the adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

Also, in order to improve the storage stability of the resin composition, it is preferable to seal the end of the main chain of the polyimide with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound. Among these, it is more preferable to use a monoamine, and examples of preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8 -Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 -aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol , 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different end groups can be introduced by reacting a plurality of end-capping agents.

-Imidation ratio (loop closure ratio)- The imidization ratio (also called "loop closure ratio") of polyimide is 70% or more from the viewpoint of the film strength and insulation properties of the obtained organic film. More than 80% is more preferable, and more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, as long as it is 100% or less. The said imidization rate is measured by the following method, for example. The infrared absorption spectrum of polyimide was measured, and the peak intensity P1 at about 1377 cm ^-1 , which was an absorption peak derived from the imide structure, was obtained. Next, after heat-treating this polyimide at 350° C. for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 at about 1377 cm ⁻¹ was obtained. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be calculated from the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

Polyimides may all contain repeating units represented by the above formula (4) containing one R ¹³¹ or R ¹³² , or may contain the above formula (4) containing two or more different types of R ¹³¹ or R ¹³² The repeating unit represented. In addition, the polyimide may contain other types of repeating units other than the repeating unit represented by the above formula (4). As another kind of repeating unit, the repeating unit represented by said formula (2), etc. are mentioned, for example.

Polyimide, for example, can be synthesized by the following method: a method of reacting tetracarboxylic dianhydride and diamine (a terminal blocking agent that replaces a part with monoamine) at low temperature; A method of reacting an anhydride (capping agent that replaces a part with an acid anhydride or a monochloride compound or a monoactive ester compound) with a diamine; a diester is obtained by tetracarboxylic dianhydride and alcohol, and then reacted with a diamine A method of reacting in the presence of a condensing agent (a part of the end-capping agent that is replaced by a monoamine); using a tetracarboxylic dianhydride and an alcohol to obtain a diester, and then chlorinating the remaining dicarboxylic acid, and A method such as a method of reacting with a diamine (an end-capping agent that replaces a part with a monoamine) to obtain a polyimide precursor, and use a known imidization reaction method to completely imidize it method; or, the method of stopping the imidization reaction in the middle and introducing a part of the imide structure; and the method of introducing a part of the imide structure by mixing the completely imidized polymer and the polyimide precursor method. In addition, other known polyimide synthesis methods can also be applied.

The weight average molecular weight (Mw) of polyimide becomes like this. Preferably it is 5,000-100,000, More preferably, it is 10,000-50,000, More preferably, it is 15,000-40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties (for example, elongation at break), it is particularly preferable that the weight average molecular weight is 15,000 or more. Moreover, the number average molecular weight (Mn) of polyimide becomes like this. Preferably it is 2,000-40,000, More preferably, it is 3,000-30,000, More preferably, it is 4,000-20,000. The molecular weight dispersion of the polyimide is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit value of the molecular weight dispersion of polyimide is not specifically defined, For example, 7.0 or less is preferable, 6.5 or less is more preferable, 6.0 or less is still more preferable. Also, when the resin composition contains a plurality of polyimides as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the plurality of polyimides described above as one resin fall within the above ranges.

式（3）中，R ¹²¹表示2價的有機基，R ¹²²表示4價的有機基，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly defined, but preferably include a repeating unit represented by the following formula (3). [chemical formula 14]

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

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), and their preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. As for dicarboxylic acid residues, only 1 type may be used, and 2 or more types may be used.

As the dicarboxylic acid residue, an aliphatic group-containing dicarboxylic acid residue and an aromatic group-containing dicarboxylic acid residue are preferable, and an aromatic group-containing dicarboxylic acid residue is more preferable. As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing straight-chain or branched (preferably straight-chain) aliphatic groups are preferred, including straight-chain or branched (preferably straight-chain) aliphatic groups A dicarboxylic acid with 2 -COOH is more preferred. The carbon number of the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and still more preferably 4 to 15 , 5-10 is particularly good. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing straight-chain aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, butanedioic acid, acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexa Fluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3- Methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoro Suberic Acid, Azelaic Acid, Sebacic Acid, Hexadecafluorosebacic Acid, 1,9-Azelaic Acid, Dodecanedioic Acid, Tridecanedioic Acid, Tetradecanedioic Acid, Pentadecanedioic Acid , Hexadecanedioic acid, Heptadecanedioic acid, Octadecanedioic acid, Nonadecanedioic acid, Eicosanedioic acid, Hexadecanedioic acid, Docosanedioic acid, Tricosane di Acid, tetracosanedioic acid, pentadecanedioic acid, hexacanedioic acid, heptacanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacanedioic acid, Hetericacanedioic acid, docosanedioic acid, diglycolic acid (diglycolic acid), and dicarboxylic acids represented by the following formulae, etc.

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [chemical formula 15]

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

As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acid having an aromatic group is preferable, and the following dicarboxylic acid containing only a group having an aromatic group and two -COOH is more preferable.

式中，A表示選自包括-CH ₂-、-O-、-S-、-SO ₂-、-CO-、-NHCO-、-C（CF ₃） ₂-及-C（CH ₃） ₂-之群組中的2價的基團，*分別獨立地表示與其他結構的鍵結部位。 [chemical formula 16]

In the formula, A represents the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ The divalent groups in the group of - and * each independently represent a bonding site with another structure.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (2), and the preferred range is also the same. R ¹²² is also preferably a group derived from a bisaminophenol derivative. As a group derived from a bisaminophenol derivative, for example, 3,3'-diamino-4,4'-di Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine Base-3,3'-dihydroxydiphenylene, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2, 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino- 3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3 ,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 ,4'-Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino- 4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

式中，X ₁表示-O-、-S-、-C（CF ₃） ₂-、-CH ₂-、-SO ₂-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價的取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R ¹²²為上述式所表示之結構亦較佳。在R ¹²²為上述式所表示之結構之情況下，在共計4個*及#中，任意2個為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且其他2個為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位，或者2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [chemical formula 17]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. In addition, it is also preferable that R ¹²² is a structure represented by the above formula. In the case where R ¹²² is the structure represented by the above formula, among the total 4 * and #, any 2 are the bonding sites of the nitrogen atom to which R ¹²² in the formula (3) is bonded and the other 2 The bonding site of the oxygen atom bonded to R ¹²² in formula (3) is preferred, and 2* are the bonding sites of the oxygen atom bonded to R ¹²² in formula (3) and 2 # is the bonding site of the nitrogen atom bonded to R ¹²² in the formula (3), or 2 * are the bonding sites of the nitrogen atom bonded to the R ¹²² in the formula (3) and 2 # It is more preferable to be the bonding site of the oxygen atom bonded to R ¹²² in the formula (3), and 2 * are the bonding sites of the oxygen atom bonded to the R ¹²² in the formula (3) and 2 # is the bonding site of the nitrogen atom bonded to R ¹²² in the formula (3), which is further preferred.

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [chemical formula 18]

In the formula (As), R ₁ is selected from a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond or the following formula Organic radicals in the group of (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different.

（式（A-sc）中，*表示與上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [chemical formula 19]

(In the formula (A-sc), * indicates that it is bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is believed that having a substituent at the ortho position of the phenolic hydroxyl group, that is, on _R3 will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and become a high temperature when hardening at low temperature. The effect of the cyclization rate is particularly good.

Also, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, it is preferable to maintain high transparency to i-rays and high cyclization rate when hardened at low temperature.

Also, in the above formula (As), R ₁ is further preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group for R1 include straight-chain or branched-chain alkyl groups having ₁ to 8 carbon atoms, which maintain high transparency to i-rays and low temperature -CH ₂ -, -CH(CH ₃ )-, - C(CH ₃ ) ₂ - is more preferred.

As the production method of the bisaminophenol derivative represented by the above-mentioned formula (A-s), for example, refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506. The content is incorporated into this manual.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, and the contents thereof are incorporated in this specification. middle. Of course, it is self-evident that it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (3). It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in terms of being able to suppress warpage accompanying ring closure.

式（SL）中，Z具有a結構和b結構，R ^1s為氫原子或碳數1～10的烴基，R ^2s為碳數1～10的烴基，R ^3s、R ^4s、R ^5s、R ^6s中的至少1個為芳香族基，其餘為氫原子或碳數1～30的有機基，其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合，亦可以為無規聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。 [chemical formula 20]

In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons, R ^2s is a hydrocarbon group with 1 to 10 carbons, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the structures a and b may be block polymerization or random polymerization. The molar % of the Z moiety is 5 to 95 molar % for the a structure, 95 to 5 molar % for the b structure, and 100 molar % for a+b.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the structure b are phenyl groups. In addition, the molecular weight of the structure represented by the formula (SL) is preferably from 400 to 4,000, more preferably from 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

When including the diamine residue represented by formula (SL) as another type of repeating unit, it is also preferable to further include, as a repeating unit, a tetracarboxylic acid residue remaining after removing an anhydride group from tetracarboxylic dianhydride. An example of such a tetracarboxylic acid residue includes an example of R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000-30,000, more preferably 20,000-29,000, further preferably 22,000-28,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 7,200-14,000, More preferably, it is 8,000-12,000, More preferably, it is 9,200-11,200. The molecular weight dispersion of the polybenzoxazole precursor is preferably at least 1.4, more preferably at least 1.5, and still more preferably at least 1.6. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly specified, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is still more preferred, and 2.2 The following are still further preferred. In addition, when the resin composition contains plural polybenzoxazole precursors as the specific resin, it is better to have a weight average molecular weight, a number average molecular weight, and a degree of dispersion of at least one polybenzoxazole precursor within the above-mentioned ranges. good. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by using the above-mentioned plurality of polybenzoxazole precursors as one resin are within the above-mentioned ranges, respectively.

式（X）中，R ¹³³表示2價的有機基，R ¹³⁴表示4價的有機基。 在具有聚合性基或酸分解性基等極性轉換基之情況下，聚合性基或酸分解性基等極性轉換基可以位於R ¹³³及R ¹³⁴中的至少一者上，如下述式（X-1）或式（X-2）所示，亦可以位於聚苯并㗁唑的末端。 式（X-1） [化學式22]

式（X-1）中，R ¹³⁵及R ¹³⁶中的至少一者為聚合性基或酸分解性基等極性轉換基，在不是聚合性基或酸分解性基等極性轉換基之情況下為有機基，其他基團與式（X）的含義相同。 式（X-2） [化學式23]

式（X-2）中，R ¹³⁷為聚合性基或酸分解性基等極性轉換基，其他為取代基，其他基團與式（X）的含義相同。 [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferable, and the following The compound represented by the formula (X) and having a polymerizable group is more preferable. As said polymerizable group, a radical polymerizable group is preferable. In addition, it may be a compound represented by the following formula (X) and having a polarity switching group such as an acid decomposable group. [chemical formula 21]

In the formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. In the case of having a polarity conversion group such as a polymerizable group or an acid decomposable group, the polarity conversion group such as a polymerizable group or an acid decomposable group can be located on at least one of R ¹³³ and R ¹³⁴ , as shown in the following formula (X- 1) or formula (X-2), it can also be located at the end of polybenzoxazole. Formula (X-1) [Chemical Formula 22]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polarity conversion group such as a polymerizable group or an acid decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid decomposable group, it is Organic group, other groups have the same meaning as formula (X). Formula (X-2) [Chemical Formula 23]

In formula (X-2), R ¹³⁷ is a polarity switching group such as a polymerizable group or an acid decomposable group, and others are substituents, and the meanings of other groups are the same as in formula (X).

The polarity conversion group such as a polymerizable group or an acid-decomposable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group of the polyimide precursor.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group is mentioned. As a specific example, the example of R ¹²¹ in the formula (3) of the polybenzoxazole precursor can be mentioned. Also, preferred examples thereof are the same as for ^R121 .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in the formula (3) of the polybenzoxazole precursor. Also, preferred examples thereof are the same as ^R122 . For example, four bonding atoms of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. In the following structures, * respectively represents a bonding site with a nitrogen atom or an oxygen atom in formula (X). [chemical formula 24]

The oxazolization rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. With the oxazolization rate of 85% or more, the shrinkage of the film due to the ring closure generated when oxazolization by heating is reduced, and the occurrence of warpage can be more effectively suppressed. The above-mentioned oxazolization rate is measured, for example, by the following method. The infrared absorption spectrum of polybenzoxazole was measured, and the peak intensity Q1 at about 1650 cm ^-1 which was the absorption peak derived from the amide structure of the precursor was obtained. Next, normalization is performed by the absorption intensity of the aromatic ring found around 1490 cm ^-1 . After heat-treating the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity Q2 at about 1650 cm ^-1 was obtained, and the absorption intensity of the aromatic ring found at about 1490 cm ^-1 was determined. standardization. Using the obtained standard values of the peak intensities Q1 and Q2, the oxazole rate of polybenzoxazole can be calculated from the following formula. Ozolization rate (%) = (standard value of peak intensity Q1/standard value of peak intensity Q2) × 100

All polybenzoxazoles may contain repeating units of the above formula (X) containing one type of R ¹³¹ or R ¹³² , or may contain the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² repeat unit. In addition, the polybenzoxazole may contain other types of repeating units in addition to the repeating units of the above-mentioned formula (X).

Regarding polybenzoxazole, for example, by making a bisaminophenol derivative and a dicarboxylic acid containing R ¹³³ or a dicarboxylic acid dichloride (dicarboxylic acid dichloride) and a dicarboxylic acid derivative selected from the above-mentioned dicarboxylic acids etc. to obtain a polybenzoxazole precursor, which is obtained by oxazolization using a known oxazole reaction method. In addition, in the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like can be used in order to improve the reaction yield or the like.

The weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and still more preferably from 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, it is particularly preferable that the weight average molecular weight is 20,000 or more. Moreover, when containing 2 or more types of polybenzoxazoles, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazoles exists in the said range. Moreover, the number average molecular weight (Mn) of polybenzoxazole becomes like this. Preferably it is 7,200-14,000, More preferably, it is 8,000-12,000, More preferably, it is 9,200-11,200. The molecular weight dispersion of the polybenzoxazole is preferably at least 1.4, more preferably at least 1.5, and still more preferably at least 1.6. The upper limit of the molecular weight dispersion of polybenzoxazole is not particularly specified, for example, it is preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, still more preferably 2.3 or less, and even more preferably 2.2 or less. Further better. In addition, when the resin composition contains a plurality of polybenzoxazoles as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polybenzoxazole are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by using the plurality of polybenzoxazoles as one resin fall within the above ranges.

式（PAI-2）中，R ¹¹⁷表示3價的有機基，R ¹¹¹表示2價的有機基，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價的有機基。 [Polyamideimide Precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [chemical formula 25]

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

In the formula (PAI-2), R ¹¹⁷ can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group or a single bond, or the A group obtained by connecting two or more of them, 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 a single bond or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group with 6 to 20 carbons or a single bond or a linking group A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferable. As the above linking group, two or more of -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylylene or these are bonded The linking group formed is preferred, and -O-, -S-, alkylene, halogenated alkylene, arylylene or a linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. As the alkylene halide, a alkylene halide having 1 to 20 carbons is preferable, an alkylene halide having 1 to 10 carbons is more preferable, and an alkylene halide having 1 to 4 carbons is more preferable. Moreover, examples of the halogen atom in the above-mentioned halogenated alkylene group include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, among which fluorine atom is preferred. The aforementioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. Examples of preferable alkylene halides include (bistrifluoromethyl)methylene and the like. As said aryl group, phenylene or naphthylene is preferable, phenylene is more preferable, and 1,3-phenylene or 1,4-phenylene is still more preferable.

Also, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound. Two of the three carboxyl groups of the tricarboxylic acid compound may be anhydrided. Examples of the tricarboxylic acid compound that may be halogenated used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used only by 1 type, and may use 2 or more types.

Specifically, the tricarboxylic acid compound includes a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a cyclic aliphatic group having 3 to 20 carbons, A tricarboxylic acid compound having an aromatic group having 6 to 20 carbons or a single bond or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group or a single bond having 6 to 20 carbons is included. A bond or a tricarboxylic acid compound of a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a linking group is more preferable.

_In addition, specific examples _of the _{tricarboxylic acid compound} include _: or phenylene-linked 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, orthophthalic acid Compounds of formic acid (or phthalic anhydride) and benzoic acid, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in formula (2), respectively, and preferred embodiments are also the same.

The polyamideimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [chemical formula 26]

In the formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In the formula (PAI-1), R ¹¹⁶ can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group or a single bond, or the A group obtained by connecting two or more of them, 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 a single bond or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group with 6 to 20 carbons or a single bond or a linking group A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferable. As the above linking group, two or more of -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylylene or these are bonded The linking group formed is preferred, and -O-, -S-, alkylene, halogenated alkylene, arylylene or a linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. As the alkylene halide, a alkylene halide having 1 to 20 carbons is preferable, an alkylene halide having 1 to 10 carbons is more preferable, and an alkylene halide having 1 to 4 carbons is more preferable. Moreover, examples of the halogen atom in the above-mentioned halogenated alkylene group include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, among which fluorine atom is preferred. The aforementioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. Examples of preferable alkylene halides include (bistrifluoromethyl)methylene and the like. As said aryl group, phenylene or naphthylene is preferable, phenylene is more preferable, and 1,3-phenylene or 1,4-phenylene is still more preferable.

Also, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present 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. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, the dicarboxylic acid dihalide is preferably a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated for use in the production of polyamideimide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide, etc. These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used only by 1 type, and may use 2 or more types.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide includes a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a Cyclic aliphatic groups, aromatic groups having 6 to 20 carbon atoms, single bonds, or groups obtained by combining two or more of these through linking groups are dicarboxylic acid compounds or dicarboxylic acid dihalides. Preferably, a dicarboxylic acid compound or a dihalogenated dicarboxylic acid containing 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 Things are better.

Further, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic di Acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, Sebacic acid, Hexadecanedioic acid, 1,9-Azelaic acid, Dodecanedioic acid, Tridecanedioic acid, Tetradecanedioic acid, Pentadecanedioic acid, Hexadecanedioic acid, Decadecanedioic acid Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid . Dodecanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'- Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of the dicarboxylic acid dihalide compound, a compound having a structure obtained by halogenating two carboxyl groups in the specific examples of the above-mentioned dicarboxylic acid compound may be mentioned.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2), and preferred embodiments are also the same.

Also, it is preferable that the polyamideimide precursor has a fluorine atom in its structure. The content of fluorine atoms in the polyamideimide precursor is preferably at least 10% by mass, and more preferably at most 20% by mass.

Also, in order to improve the adhesion to the substrate, the polyamideimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as a diamine component, the aspect which used bis(3-aminopropyl) tetramethyldisiloxane, bis(p-aminophenyl) octamethyl pentasiloxane, etc. is mentioned.

As an embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) and the compound represented by the formula (2) can be mentioned. The total content of the repeating units indicated is an aspect of 50 mol% or more of all the repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamide imide precursor except the terminal can be the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1) Any one of the repeating unit and the repeating unit represented by formula (2). Also, as another embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned. It is the form of more than 50 mol% of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyamide imide precursor except the terminal can be the repeating unit represented by the formula (PAI-2) or the repeating unit represented by the formula (PAI-1) any of the repeating units.

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000-500,000, more preferably 5,000-100,000, further preferably 10,000-50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000. The molecular weight dispersion of the polyamideimide precursor is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the molecular weight dispersion of the polyamideimide precursor is not particularly defined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. In addition, when the resin composition contains a plurality of polyamide imide precursors as a specific resin, the weight average molecular weight, number average molecular weight and dispersion of at least one polyamide imide precursor are within the above range is better. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by using the plurality of polyamideimide precursors as one resin fall within the above ranges, respectively.

〔Polyamideimide〕 The polyamidoimide used in the present invention may be an alkali-soluble polyamidoimide, or may be a polyamidoimide soluble in a developing solution mainly composed of an organic solvent. In this specification, an alkali-soluble polyamide imide refers to a polyamide imide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C, and is considered from the viewpoint of pattern formation. It is preferred to dissolve more than 0.5 g of polyamide imide, and it is still more preferable to dissolve more than 1.0 g of polyamide imide. The upper limit of the above-mentioned dissolved amount is not particularly limited, but is preferably 100 g or less. Also, from the viewpoint of the film strength and insulating properties of the obtained organic film, the polyamide imide is a polyamide imide having a plurality of amide bonds and a plurality of amide structures on the main chain. better.

-Fluorine atoms- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyamideimide has a fluorine atom. A fluorine atom, for example, is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below, and as a fluorinated alkyl group contained in the repeating unit represented by the formula (PAI-3) described below. R ¹¹⁷ or R ¹¹¹ is more preferred. The amount of fluorine atoms is preferably at least 5% by mass and preferably at most 20% by mass relative to the total mass of polyamideimide.

-Ethylenically unsaturated bond- From the viewpoint of the film strength of the obtained organic film, polyamideimide may have an ethylenically unsaturated bond. Polyamideimide may have an ethylenically unsaturated bond at the main chain terminal or may have an ethylenically unsaturated bond at the side chain, but preferably has an ethylenically unsaturated bond at the side chain. It is preferable that the said ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the following formula (PAI-3), and it is contained in the following formula (PAI-3) as a group having an ethylenically unsaturated bond R ¹¹⁷ or R ¹¹¹ in the repeating unit represented is more preferred. The preferable aspect of the group which has an ethylenically unsaturated bond is the same as the preferable aspect of the group which has an ethylenically unsaturated bond in the said polyimide.

The amount of ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g, based on the total mass of polyamideimide.

-Polymerizable group other than ethylenically unsaturated bond- The polyamideimide may have a polymerizable group other than ethylenically unsaturated bond. Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the above-mentioned polyimide. Polymerizable groups other than ethylenically unsaturated bonds are preferably included in R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, for example. The amount of polymerizable groups other than ethylenically unsaturated bonds is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g, based on the total mass of polyamide imide.

-Polarity conversion group- The polyamideimide may have a polarity conversion group, such as an acid-decomposable group. The acid-decomposable groups in the polyamideimide are the same as the acid-decomposable groups described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred aspects are also the same.

-acid value- In the case of using polyamide imide for alkali development, from the viewpoint of improving developability, the acid value of polyamide imide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, 70 mgKOH/g or more is still more preferable. Moreover, the above-mentioned acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less. In addition, when polyamide imide is used for development using a developing solution mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of polyamide imide is 2 to 50%. 35 mgKOH/g is preferable, 3-30 mgKOH/g is more preferable, 5-20 mgKOH/g is still more preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acidic group contained in a polyamideimide, the group similar to the acidic group in the said polyimide can be mentioned, and a preferable aspect is also the same.

-Phenolic hydroxyl group- It is preferable that polyamide imide has a phenolic hydroxyl group from a viewpoint of making the developing speed by alkali developing solution suitable. Polyamideimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group on the side chain. The phenolic hydroxyl group is preferably included in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later. The amount of phenolic hydroxyl groups is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g, based on the total mass of the polyamideimide.

式（PAI-3）中，R ¹¹¹及R ¹¹⁷分別與式（PAI-2）中的R ¹¹¹及R ¹¹⁷的含義相同，較佳態樣亦相同。 在具有聚合性基之情況下，聚合性基可以位於R ¹¹¹及R ¹¹⁷中的至少一者上，亦可以位於聚醯胺醯亞胺的末端。 The polyamidoimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it includes repetitions represented by the following formula (PAI-3). unit is preferred. [chemical formula 27]

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same. In the case of having a polymerizable group, the polymerizable group may be located on at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at a terminal of polyamideimide.

Also, in order to improve the storage stability of the resin composition, it is preferable to seal the end of the main chain of polyamideimide with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound. A preferable aspect of the end-blocking agent is the same as that of the above-mentioned end-blocking agent in polyimide.

-Imidation rate (ring closure rate)- From the viewpoints of film strength and insulation of the obtained organic film, the imidization rate (also referred to as "loop closure rate") of polyamide imide is preferably 70% or more, and 80% or more is more preferable. Good, more than 90% is better. The upper limit of the above-mentioned imidization rate is not particularly limited, as long as it is 100% or less. The above-mentioned imidization rate was measured by the same method as the ring-closure rate of the above-mentioned polyimide.

Polyamide imides may all contain repeating units represented by the above formula (PAI-3) containing one R ¹¹¹ or R ¹¹⁷ , or may contain two or more different types of R ¹³¹ or R ¹³² . The repeating unit represented by the formula (PAI-3). In addition, the polyamideimide may contain other types of repeating units other than the repeating unit represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above-mentioned formula (PAI-1) or formula (PAI-2), and the like.

Polyamidoimide can be synthesized by, for example, a method in which a polyamidoimide precursor is obtained by a known method and completely imidized using a known imidization reaction method. method; or, a method of stopping the imidization reaction in the middle, and introducing a part of the imide structure; and introducing a part of the imide by mixing the completely imidized polymer and the polyamidoimide precursor method of structure.

The weight average molecular weight (Mw) of polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, it is particularly preferable that the weight average molecular weight is 20,000 or more. In addition, the number average molecular weight (Mn) of the polyamideimide is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and still more preferably from 4,000 to 25,000. The molecular weight dispersion of polyamideimide is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the molecular weight dispersion of polyimide is not specifically defined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. Also, when the resin composition contains a plurality of polyamideimides as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyamideimide are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural kinds of polyamideimides as one resin are within the above-mentioned ranges, respectively.

〔Manufacturing method of polyimide precursor etc.〕 Polyimide precursors and the like can be obtained by, for example, a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and obtaining polyimide by reacting tetracarboxylic dianhydride and diamine at low temperature. A method of esterifying an amine acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent, by Tetracarboxylic dianhydride and alcohol to obtain a diester, and then use a halogenating agent to halogenate the remaining dicarboxylic acid and react it with a diamine, etc. Among the above production methods, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferable. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. Examples of the halogenating agent include sulfuryl chloride, oxalyl chloride, phosphorus oxychloride, and the like. In the production method of polyimide precursor etc., it is preferable to use an organic solvent when carrying out a reaction. The organic solvent may be one type, or two or more types. The organic solvent can be appropriately set depending on the raw material, but examples include pyridine, diglyme (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate , Dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor etc., it is preferable to add a basic compound at the time of reaction. The basic compound may be one type, or two or more types. The basic compound can be appropriately set depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Dimethyl-4-aminopyridine, etc.

-Encapping agent- In the production method of polyimide precursor etc., in order to further improve the storage stability, it is preferable to seal the carboxylic anhydride, acid anhydride derivative or amine group remaining at the terminal of resin such as polyimide precursor. When sealing the carboxylic acid anhydride and acid anhydride derivatives remaining at the end of the resin, monohydric alcohols, phenols, mercaptans, thiophenols, monoamines, etc. can be used as end-capping agents. From the viewpoint of reactivity and film stability , It is better to use monohydric alcohol, phenols or monoamine. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloro Methanol, furfuryl alcohol and other primary alcohols, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary butanol, adamantanol and other tertiary alcohols alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. In addition, preferred compounds of 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, 1-carboxy-5-aminonaphthalene, 2-carboxy-7- Aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminobenzoic acid Cylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different end groups can be introduced by reacting a plurality of end-capping agents. In addition, when sealing the amine group at the terminal of the resin, it can be sealed with a compound having a functional group capable of reacting with the amine group. The preferred sealants for amino groups are carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc., and carboxylic anhydride and carboxylic acid chloride are more preferred . Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic anhydride, etc. Also, as preferred compounds of carboxylic acid chlorides, acetyl chloride, acryl chloride, propionyl chloride, methacryl chloride, trimethylacetyl chloride, cyclohexaneformyl chloride, 2-ethyl Hexylhexyl chloride, cinnamonyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc.

-Solid precipitation- When producing a polyimide precursor and the like, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as required, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer is formed. It is analyzed and precipitated as a solid, and dried to obtain a polyimide precursor and the like. In order to increase the degree of purification, operations such as redissolving polyimide precursors, reprecipitation, and drying may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

〔content〕 The content of the specific resin in the resin composition of the present invention is preferably at least 20% by mass, more preferably at least 30% by mass, more preferably at least 40% by mass, and even more preferably at least 50% by mass, based on the total solid content of the resin composition. The above are further preferred. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and 97% by mass relative to the total solid content of the resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When containing 2 or more types, it is preferable that a total amount exists in the said range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but preferably contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, two resins different in structure derived from dianhydride (R ¹¹⁵ described in the above formula (2)) that are polyimide precursors are included. More than one polyimide precursor is preferred.

<Other resins> The resin composition of the present invention may contain other resins (hereinafter also simply referred to as “other resins”) different from the specific resin as resin. Moreover, it is also possible to set it as the aspect containing specific resin and other resin. Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, and urethane resins. , butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in applicability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained. For example, instead of the polymerizable compound described later or in addition to the polymerizable compound described later, one with a weight average molecular weight of 20,000 or less has a high polymerizable group value (for example, the polymerizable group content molar amount in 1 g of resin is 1×10 ⁻³ Mole/g or more) (meth)acrylic resin can be added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 1% by mass or more, relative to the total solid content of the resin composition. Preferably, 2% by mass or more is still more preferably, 5% by mass or more is still more preferably, and 10% by mass or more is still more preferably. The content of other resins in the resin composition of the present invention is preferably at least 20% by mass, more preferably at least 30% by mass, more preferably at least 40% by mass, and even more preferably at least 50% by mass, based on the total solid content of the resin composition. The above are further preferred. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and 97% by mass relative to the total solid content of the resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. Also, when the resin composition of the present invention contains specific resins and other resins, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass relative to the total solid content of the resin composition. It is further preferably at most 60 mass %, still more preferably at most 60 mass %, still more preferably at most 50 mass %, can also be 40 mass % or less, and can further be 30 mass % or less. Moreover, as a preferable aspect of the resin composition of this invention, it can also be set as the aspect which contains specific resin, and content of other resin is low. In the above aspects, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, still more preferably 10 mass % or less, and 5 mass % or less with respect to the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the said content is not specifically limited, What is necessary is just to be 0 mass % or more. The resin composition of this invention may contain only 1 type of other resins, and may contain 2 or more types. When containing 2 or more types, it is preferable that a total amount exists in the said range.

Among them, it is preferable that the resin composition of the present invention contains at least one resin selected from the group consisting of specific resins, phenol resins, and epoxy resins. The phenolic resin may be any of a resole type and a novolak type, and specifically, cresol novolac resins, catechol novolak resins, resorcinol novolak resins, hydrogen Quinone novolaks, catechol resorcinol novolac resins, resorcinol hydroquinone novolac resins, and the like. The epoxy resin is not particularly limited, but examples include novolac-type epoxy resins, bisphenol-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ether-type epoxy resins, and trisphenolmethane-type epoxy resins. Resin, Trisphenol propane type epoxy resin, Alkyl modified trisphenol methane type epoxy resin, Epoxy resin containing triphenol core, Dicyclopentadiene modified phenol type epoxy resin, Naphthol type epoxy resin , naphthalene type epoxy resin, novolac aralkyl type epoxy resin having at least any one of phenylene skeleton and biphenylene skeleton, at least one of having at least one of phenylene skeleton and biphenylene skeleton Aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins, aliphatic epoxy resins, and the like.

＜Polymerizable compound＞ It is preferable that the resin composition of this invention contains a polymeric compound. Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

Moreover, it is also preferable that the resin composition (especially, the 2nd resin composition) of this invention contains the compound containing an aromatic polycyclic structure, a fluorine-containing compound, or the compound which has a siloxane group. Wiring (copper, etc.) is arranged on the second resin composition, so that the second resin composition itself that is in direct contact with the wiring has characteristics such as improving the electrical performance of the wiring, such as a second resin with a low dielectric constant. Composition is preferred. Therefore, the compounds included in the second resin composition are compounds containing aromatic polycyclic structures such as fennel skeleton and polyphenylene skeleton, 4,4'-diamino-2,2'-bis(trifluoromethyl ) biphenyl, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and other fluorine-containing compounds or compounds derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane The relative permittivity of a siloxane-based compound such as oxane when a film is formed by itself is preferably less than 3.0, more preferably 2.8 or less, and still more preferably 2.6 or less. The lower limit of the relative permittivity is not particularly limited, as long as it is 0 or more. When a film is formed from the above compound, the loss tangent is preferably 0.01 or less, more preferably 0.005 or less, and still more preferably 0.002 or less. The lower limit of the above-mentioned loss tangent is not particularly limited, as long as it is 0 or more. Accordingly, the second resin composition preferably includes a compound having a polymerizable group and an aromatic polycyclic structure, and more preferably includes a compound having a polymerizable group and a skeletal skeleton. Among them, it is preferable that the dielectric coefficient of the above compound is smaller than that of the resin contained in the second resin composition. Specifically, the difference between the relative permittivity when the film is formed from the above-mentioned resin and the relative permittivity when the film is formed from the above-mentioned compound is preferably 0.2 or more, more preferably 0.4 or more.

The aromatic group in the polymerizable compound having an aromatic group may be monocyclic or polycyclic, but polycyclic is preferred, and condensed ring is more preferred. Examples of the aromatic polycyclic structure include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fenene ring structures, and acenaphthene ring structures. It is not limited to this.

〔Free radical crosslinking agent〕 The resin composition of the present invention preferably contains a free radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryl, maleimide, (meth)acryl A group having an ethylenically unsaturated bond such as an amino group. Among them, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferable as the above-mentioned group containing an ethylenically unsaturated bond. From the viewpoint of reactivity, (Meth)acryloyl is more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having 2 or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 10 ethylenically unsaturated bonds are more preferred. 6 compounds are further preferred. Also, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. better.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, acyl acids, etc. The amines are preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxies can also be preferably used. Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. Also, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, as well as those with halogen groups or Substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as toluenesulfonyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, it is also possible to use a compound group replaced with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and these contents are incorporated into this specification.

Moreover, it is also preferable that a radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tri (Meth)acrylate, Neopentylthritol tetra(meth)acrylate, Dineopentylthritol penta(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Hexylene glycol di( Meth)acrylate, trimethylolpropane tri(acryloxypropyl)ether, tris(acryloxyethyl)isocyanurate, glycerin or trimethylolethane etc. Compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols followed by (meth)acrylic esterification, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Laid-Open (Meth)acrylic acid amine esters described in the gazettes of Sho 51-037193, JP-A-48-064183, JP-A-49-043191, JP-A-52-030490 Polyester acrylates, polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Also, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, the polyfunctional (meth)acrylate obtained by making the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid, etc. are also mentioned.

Also, as preferred radical crosslinking agents other than the above, those described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. can also be used. A compound or a cardo resin having an oxene ring and having two or more ethylenically unsaturated bond-containing groups.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or Japanese Patent Laid-Open No. 02 - Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. Moreover, the compound containing a perfluoroalkyl group as described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the etc. are included in this manual.

In addition, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds described as formula (1) and formula (2) together with their specific examples can also be used as radical crosslinking agents. A compound obtained by adding ethylene oxide or propylene oxide to (meth)acrylate.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the radical crosslinking agent, and these contents are incorporated in this specification.

As a radical crosslinking agent, diperythritol triacrylate (as a commercial item is KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), diperythritol tetraacrylate (as a commercial item KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), diperythritol penta(meth)acrylate (commercially available KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.), diperythritol hexa(meth)acrylate (a commercially available product is KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A- DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and a structure in which the (meth)acryl groups are bonded via ethylene glycol residues or propylene glycol residues are preferable. These oligomer types can also be used.

Commercially available free radical crosslinking agents include, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxylate chains, and SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains. Sartomer Company, Inc. SR-209, 231, 239 of functional methyl acrylate, Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, trifunctional acrylate of isobutoxy chain, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA -306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a free radical crosslinking agent, such as Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Acrylates, 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 have an oxirane-based skeleton. The urethane compounds are also preferred. Furthermore, as a radical crosslinking agent, it is also possible to use those having an amino group in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-01-105238. Compounds with structure or sulfide structure.

The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent with acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which reacts a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Especially preferably, in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is neopentyl glycol or di-neopentyl tetra Alcohol compounds. As a commercial item, M-510, M-520, etc. are mentioned, for example as a polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD.

As described above, it is also preferable to use a compound containing an aromatic polycyclic structure as the radical crosslinking agent. Examples of radical crosslinking agents having an aromatic polycyclic structure include 1,3-divinylnaphthalene, acenaphthene, and 9,9-bis[4-[2-(acryloxy)ethoxy] Phenyl]-9H-fennel, 9,9-bis[4-[2-[2-(acryloyloxy)ethoxy]ethoxy]phenyl]-9H-fennel, compounds with the following structures, etc. . [chemical formula 28]

As a commercial item, Osaka Gas Chemicals Co., LTD. make, OGSOL EA-0200, EA-300, GA-2800, GA-5000, GA-5060P, EA-F5710, EA-HR033 etc. are mentioned, for example.

The preferred acid value of the free radical crosslinking agent with acid groups is 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of a radical crosslinking agent exists in the said range, it will be excellent in workability|operativity in manufacture, and also will be excellent in developability. Also, the polymerizability is good. About the said acid value, it measured based on description of JISK0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use bifunctional methacrylate or acrylate for the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate ester, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate , dimethyloltricyclodecane diacrylate, dimethyloltricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylates with other amine ester bonds, bifunctional methacrylate with amine ester bonds base acrylate. These can mix and use 2 or more types as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 polyethylene glycol chains. In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage with control of the modulus of elasticity of the pattern (cured product). As monofunctional radical crosslinking agents, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol(meth)acrylamide, epoxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, vinylglycidyl ether, and the like. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable. In addition, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned as a difunctional or more radical crosslinking agent.

When containing a radical crosslinking agent, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably at least 5% by mass. The upper limit is more preferably at most 50% by mass, and more preferably at most 30% by mass.

A radical crosslinking agent may be used individually by 1 type, and may mix and use 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount falls within the said range.

〔Other crosslinking agents〕 It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above radical crosslinking agents. In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned radical cross-linking agents, which have a plurality of cross-linking agents in the molecule that are promoted by the photosensitization of the above-mentioned photoacid generator or photobase generator. The compound that forms a covalent bond reaction group between other compounds or their reaction products in the composition is preferred, and has a plurality of compounds in the molecule that are promoted by the action of acid or base with other compounds or other compounds in the composition. Compounds of reactive groups that form covalent bonds between reaction products are preferred. It is preferable that the above-mentioned acid or base is an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl groups are preferred, and compounds having groups selected from the group consisting of acyloxymethyl A compound having a structure in which at least one group of the group consisting of hydroxymethyl, alkoxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. As other crosslinking agents, for example, formaldehyde or formaldehyde and alcohol can be exemplified by reacting compounds containing amino groups such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., through acyloxymethyl, A compound in which the hydrogen atom of the above amino group is substituted with a methylol or alkoxymethyl group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, it may be an oligomer formed by self-condensing the methylol groups of these compounds. A cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and a cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. A crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents, including glycoluril-based cross-linking agents as described later. At least one compound selected from the group consisting of crosslinking agents and melamine-based crosslinking agents is more preferred.

As a compound containing at least one of the alkoxymethyl group and the acyloxymethyl group in the present invention, the compound in which the alkoxymethyl group or the acyloxymethyl group is directly attached to the aromatic group or the following urea structure can be mentioned. Compounds substituted on a nitrogen atom or on a trichodium atom are examples of structures. The alkoxymethyl group or acyloxymethyl group possessed by the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6. The molecular weight of the above compound is preferably 1500 or less, more preferably 180-1200.

[chemical formula 29]

R ₁₀₀ represents an alkyl or acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include various compounds of the following general formula.

[chemical formula 30]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl or acyl group, and R ₁₀₃ represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl or The action of decomposing to produce alkali-soluble groups (for example, the group detached by the action of acid, the group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or An alkyl group with 1 to 4 carbon atoms, R ⁵ represents a group that is detached by the action of an acid.)). R ₁₀₅ each independently represent an alkyl or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. With regard to the group decomposed by the action of an acid to produce an alkali-soluble group, the group detached by the action of an acid, and R ⁵ in the group represented by -C(R ⁴ ) ₂ COOR ⁵ , for example, -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be either linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The above-mentioned cycloalkyl group may have a monocyclic structure or may have a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The aforementioned aralkyl group refers to an aryl group substituted with an alkyl group, and preferred aspects of the alkyl group and aryl group are the same as those of the above-mentioned alkyl group and aryl group. The aforementioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. In addition, these groups may have known substituents within the range in which the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As a group that is decomposed by the action of an acid to produce an alkali-soluble group or a group that is detached by the action of an acid, tertiary alkyl ester groups, acetal groups, cumyl ester groups, and enol esters are preferred Base etc. Further preferred are tertiary alkyl ester groups and acetal groups.

As a compound which has an alkoxymethyl group, the following structures are mentioned specifically. Examples of compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds is changed to an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following various compounds, but are not limited thereto.

[chemical formula 31]

[chemical formula 32]

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used. From the standpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a tricyclic ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of urea-based crosslinking agents include monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, monomethoxy Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethyl Hydroxyl glycoluril, Triethoxymethylated glycoluril, Tetraethoxymethylated glycoluril, Monopropoxymethylated glycoluril, Dipropoxymethylated glycoluril, Tripropoxymethylated glycoluril methylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril or tetrabutoxymethylated glycoluril glycoluril-based cross-linking agent such as glycoluril; Bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and other urea-based crosslinking agents, Monomethylolated ethyl urea or dimethylolated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea ethylidene urea-based cross-linking agent such as methylated ethylurea, Monomethylolated propyl urea, Dimethylolated propyl urea, Monomethoxymethylated propyl urea, Dimethoxymethylated propyl urea, Monoethoxymethylated propyl urea , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethyl Propylene urea-based cross-linking agents such as alkylated propylene urea, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of benzoguanamine-based crosslinking agents include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, and tetramethylolated benzoguanamine. methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine Benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it is also preferable to use a compound directly bonded to an aromatic ring (preferably a benzene ring). A compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(methylol)cresol, bis(methylol)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(methylol) base) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)benzene (methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyloxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl ‐1,3‐benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

Commercially available products can also be used as other crosslinking agents, and preferred commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION above), 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, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (above Sanwa Chemical Co., Ltd.), etc.

Also, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxetane compounds as other crosslinking agents.

-Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes cross-linking reaction below 200°C, and there is no dehydration reaction caused by cross-linking, so it is not easy to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing the low-temperature hardening and warpage of the resin composition of this invention.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further lowered, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butyl Diol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, etc., alkylene glycol type epoxy resin or polyol hydrocarbon type epoxy resin; polypropylene glycol diglycidyl ether Polyalkylene glycol-type epoxy resins such as glyceryl ether; epoxy epoxy-based silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, 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) Trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by 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 Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100 , CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN -104S, CER-1020, EPPN-201, BREN-S, BREN-10S (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 (above, Nagase Che mtex Corporation), etc. Moreover, the following compounds can also be preferably used.

[chemical formula 33]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

Among the above structures, it is preferable that n is 1-2 and m is 3-7 from the viewpoint of achieving both heat resistance and elongation.

Among them, as described above, it is also preferable that the resin composition (especially, the second resin composition) of the present invention contains a polymerizable compound having an aromatic polycyclic structure as the polymerizable compound. As an epoxy compound which has an aromatic polycyclic structure, the compound of the following structure is mentioned, for example. [chemical formula 34]

-Oxetane compounds (compounds having an oxetane group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzene dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used individually or in mixture of 2 or more types.

-Benzozoline compounds (compounds having a benzoxazolyl group)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzo 㗁 𠯤 compound does not generate outgassing during hardening, thereby further reducing heat shrinkage and suppressing generation of warpage, so it is preferable.

Preferable examples of benzodiazepine compounds include P-d type benzodiazepines, F-a type benzodiazepines (the above are product names, manufactured by Shikoku Chemicals Corporation), and polyhydroxystyrene resin benzodiazepines. Adducts, novolak-type dihydrobenzo㗁𠯤 compounds. These can be used individually or in mixture of 2 or more types.

The content of other crosslinking agents 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 1.0 to 10% by mass relative to the total solid content of the resin composition of the present invention. Quality % is especially good. Other crosslinking agents may contain only 1 type, and may contain 2 or more types. When two or more kinds of other crosslinking agents are contained, it is preferable that the total thereof is within the above-mentioned range.

〔polymerization initiator〕 It is preferable that the resin composition of the present invention contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. It does not specifically limit as a photoradical polymerization initiator, It can select suitably from well-known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to rays from an ultraviolet region to a visible region is preferable. In addition, it may also be an active agent that has some interaction with a photoexcited sensitizer to generate active free radicals.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient 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 a compound can be measured using a known method. For example, it is preferable to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) and measure at a concentration of 0.01 g/L using ethyl acetate solvent.

As a photoradical polymerization initiator, a well-known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (such as compounds having a trioxadiazole skeleton, compounds having a oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl compounds such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Regarding such details, the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the content is incorporated into this specification. In addition, examples include paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in JP-A-6301489, and those described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in the Publication No. 2019-044030, the photopolymerization initiator described in the Japanese Patent Application Publication No. 2019-044030, and the peroxide-based initiator described in the Japanese Patent Application Publication No. 2019-167313, And these contents are also compiled into this manual.

As the ketone compound, for example, compounds described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and the content thereof is incorporated in the present specification. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as photoradical polymerization initiators, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969, an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898, and This content is incorporated into this manual.

As the α-hydroxy ketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (product name: both made by BASF).

As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all made by BASF) can be used. system).

As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used, and the content is incorporated in this specification.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819, or IRGACURE-TPO (product names: both are manufactured by BASF Corporation) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.

More preferably, an oxime compound is mentioned as a photoradical polymerization initiator. By using an oxime compound, exposure latitude can be improved more effectively. Since an oxime compound has a wide exposure latitude (exposure margin) and functions also as a photocuring accelerator, it is especially preferable.

Specific examples of oxime compounds include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, compounds described in JP 2006-342166 A, Compounds, Compounds described in J.C.S.Perkin II (1979, pp.1653-1660), Compounds described in J.C.S.Perkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, compounds described in JP-A-2004-534797, JP-A-2017-019766 Compounds described, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, Japanese Patent Application Publication No. 2017-198865 The compounds described in, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compounds described in International Publication No. 2013/167515, etc., are incorporated into this specification.

Examples of preferred oxime compounds include compounds of the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino) ) butane-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentane-3-one, 2- (Acetyloxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-( (4-tosyloxy)imino)butan-2-one and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime-based radical photopolymerization initiator) as a radical photopolymerization initiator. The oxime photoradical polymerization initiator has a >C=N-O-C(=O)- linking group in the molecule.

[chemical formula 35]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, JP 2012- Photoradical polymerization initiator 2) described in the 014052 publication. In addition, 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) can also be used . Also, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Moreover, the oxime compound of the following structures can also be used. [chemical formula 36]

An oxime compound having an oxene ring can also be used as a photoradical polymerization initiator. Specific examples of the oxime compound having an oxene ring include the compounds described in JP-A-2014-137466 and the compounds described in JP-A-06636081, the contents of which are incorporated herein.

As a photoradical polymerization initiator, the oxime compound which has a skeleton in which at least one benzene ring in a carbazole ring becomes a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505, and the content is incorporated in this specification.

Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, JP Compound (C-3) and the like described in Paragraph 0101 of Publication No. 2013-164471, etc., are incorporated into this specification.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferred that the oxime compound having a nitro group be a dimer. Specific examples of oxime compounds having a nitro group include those described in paragraphs 0031 to 0047 of JP-A-2013-114249 , and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466 . Compounds, compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and the contents thereof are incorporated in this specification. Moreover, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.

An oxime compound having a benzofuran skeleton can also be used as a photoradical polymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

An oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used as the photoradical polymerization initiator. Examples of such a photopolymerization initiator include compounds described in International Publication No. 2019/088055, and the contents thereof are incorporated in this specification.

As the photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 having an electron-withdrawing group introduced into an aromatic ring can also be used. Examples of the electron-withdrawing group included in the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group, and a nitro group are preferable, and an acyl group is more preferable, and a benzoyl group is still more preferable from the viewpoint of easy formation of the film excellent in light resistance. The benzoyl group may have a substituent. As a substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic epoxy group, an alkenyl group, an alkylthio group, an arylthio group , acyl group or amino group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic epoxy group, alkylthio group, arylthio group or amino group are more preferred, alkoxy group, alkyl group A thio group or an amino group is further preferred.

式中，R ^X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、亞膦醯基、胺甲醯基或胺磺醯基， R ^X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R ^X3～R ^X14分別獨立地表示氫原子或取代基； 其中，R ^X10～R ^X14中的至少1個為拉電子基團。 It is preferable that the oxime compound OX is at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and the compound represented by the formula (OX2) is more preferable. [chemical formula 37]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic epoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aromatic Sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group, R ^X2 represents alkyl, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic epoxy group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group group, arylsulfonyl group, acyloxy group or amino group, R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent; wherein, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, and the contents thereof are incorporated in the present specification.

Preferred oxime compounds include oxime compounds having specific substituents disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group disclosed in JP-A-2009-191061, etc. , and incorporate this content into this manual.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyl trisulfone compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl Compounds in the group of -benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Further preferred photo-radical polymerization initiators are trihalomethyl trisulfone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds are selected from the group consisting of trihalomethyl trisulfone compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, diphenylmethane It is still more preferable to use at least one kind of compound in the group of ketone compounds, and it is still more preferable to use a metallocene compound or an oxime compound.

In addition, as the photoradical polymerization initiator, N, such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ,Aromatic ketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, quinones formed by condensation with aromatic rings such as alkyl anthraquinones, Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Moreover, the compound represented by following formula (I) can also be used.

[chemical formula 38]

In formula (I), R ^I00 is an alkyl group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbons, or a phenyl group Or alkyl with 1 to 20 carbons, alkoxy with 1 to 12 carbons, halogen atom, cyclopentyl, cyclohexyl, alkenyl with 2 to 12 carbons, interrupted by one or more oxygen atoms A phenyl or biphenyl group substituted by at least one of an alkyl group with 2 to 18 carbons and an alkyl group with 1 to 4 carbons, R ^I01 is a group represented by formula (II) or the same as R ^I00 R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen atom.

[chemical formula 39]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

Moreover, the compound described in paragraph 0048-0055 of International Publication No. 2015/125469 can also be used as a photoradical polymerization initiator, and this content is incorporated in this specification.

As the radical photopolymerization initiator, a difunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a radical photopolymerization initiator, two or more radicals are generated from 1 molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is lowered, solubility in a solvent or the like is improved, precipitation becomes difficult over time, and the temporal stability of the resin composition can be improved. Specific examples of photoradical polymerization initiators with bifunctional or trifunctional or higher functions include JP 2010-527339 A, JP 2011-524436 A, International Publication No. 2015/004565, JP Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table No. 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds described in Japanese Patent Publication No. 2013-522445 (E ) and compound (G), Cmpd 1-7 described in International Publication No. 2016/034963, the oxime ester photoinitiator described in paragraph 0007 of JP 2017-523465, JP 2017- Photoinitiators described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 167399, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, and Japanese Patent Publication No. 6469669 The oxime ester photoinitiator etc. are described, and the content is compiled into this specification.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass, more preferably 1.0 to 10% by mass. A photoinitiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that a total amount exists in the said range. In addition, since a photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by a photopolymerization initiator may further progress by heating, such as an oven or a hot plate.

〔Sensitizer〕 The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in an electronically excited state contacts with thermal radical polymerization initiators, photoradical polymerization initiators, etc., thereby producing electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator cause a chemical change and decompose to generate radicals, acids, or bases. As the sensitizer that can be used, benzophenone series, michelerone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenanthrazole series, pyrrolopyrazole azomethine series Compounds such as the Kou Yamaguchi system, the phthalocyanine system, the benzopyran system, and the indigo system. Examples of sensitizers include Michelerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentadiene, alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-di Methylaminobenzylidene indanone, 2-(p-Dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-Dimethylaminophenylvinylidene)benzo Thiazole, 2-(p-dimethylaminophenylethenylidene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4' -diethylaminobenzylidene) 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 ester, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-di Methylaminostyryl)benzothiazole, 2-(p-Dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-Dimethylaminobenzoyl) Styrene, diphenylacetamide, benzamide, N-methylacetamide, 3',4'-dimethylacetamide, etc. Also, other sensitizing dyes can be used. For details of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, and the content is incorporated in this specification.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.5 to 10% by mass relative to the total solid content of the resin composition. for further improvement. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the third edition of Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH and GeH in the molecule, and a group of compounds for RAFT (Reversible Addition Fragmentation chain Transfer: Reversible addition chain transfer polymerization) polymerized thiolthio group dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc. These can generate free radicals by donating hydrogen to low-activity free radicals or can generate free radicals by deprotonation after being oxidized. In particular, thiol compounds can be preferably used.

In addition, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used, and the content is incorporated in this specification.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention. More preferably, 0.5-5 mass parts is still more preferable. The chain transfer agent may be only 1 type, or may be 2 or more types. When there are two or more kinds of chain transfer agents, it is preferable that the total thereof is within the above-mentioned range.

＜Thermal polymerization initiator＞ It is also preferable that the resin composition of the present invention contains a thermal polymerization initiator. In particular, by including the thermal polymerization initiator in the second resin composition, for example, in the second pre-heating step or the second post-heating step, polymerization of the polymerizable compound can be accelerated. As a thermal polymerization initiator, it can be selected according to the kind of polymerizable compound, but a thermal radical polymerization initiator is preferable. A thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. Moreover, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Examples of the thermal polymerization initiator include known azo compounds, known peroxide compounds, and the like. Examples of the azo-based compound include azobis-based compounds. The azo compound may be a compound having a cyano group or a compound not having a cyano group. Examples of peroxide compounds include ketone peroxide, peroxy acetal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxy acetal Oxidized esters, etc. Commercially available products can also be used as the thermal polymerization initiator, and examples thereof include V-40, V-601, VF-096 manufactured by FUJIFILM Wako Pure Chemical Corporation, and PERHEXYL O, PERHEXYL D, PERHEXYL I, and PERHEXA manufactured by NOF CORPORATION. 25O, PERHEXA 25Z, PERCUMYL D, PERCUMYL D-40, PERCUMYL D-40MB, PERCUMYL H, PERCUMYL P, PERCUMYL ND, etc. Moreover, as a thermal radical polymerization initiator, specifically, the compound described in paragraph 0074-0118 of Unexamined-Japanese-Patent No. 2008-063554 is mentioned, and this content is incorporated in this specification.

The content of the thermal polymerization initiator in the resin composition (especially, the second resin composition) is preferably 0.05 mass % or more and 10 mass % or less with respect to the total solid content of the second resin composition, 0.1 mass % % or more and 10 mass % or less are more preferable, 0.1 mass % or more and 5 mass % or less are more preferable, and 0.5 mass % or more and 3 mass % or less are especially preferable. The resin composition (especially, the second resin composition) may contain one type of thermal polymerization initiator alone, or may contain two or more types. When containing 2 or more types, it is preferable that the total amount is in the said range.

〔Photoacid generator〕 The resin composition of the present invention preferably contains a photoacid generator. The photoacid generator means a compound that generates at least one of Brenest's acid and Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, a photoacid generator capable of generating acid by exposure to light is preferred. Examples of the generated acid include preferably hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives , antimony derivatives, halogen peroxide, sulfonamide, etc.

Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, onium salt compounds, etc. . From the viewpoint of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable, and from the viewpoint of mechanical properties of the formed film, etc., oxime esters are preferable.

Examples of quinone diazide compounds include those obtained by bonding sulfonate esters of quinone diazide to monovalent or polyvalent hydroxy compounds, and sulfonic acids of quinone diazides bonded to monovalent or polyvalent hydroxy compounds via sulfonamides. amine compounds, those obtained by sulfonic acid of quinonediazide bonded to polyhydroxypolyamine compounds through ester bond and/or sulfonamide bond, etc. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxypolyamine compounds may not be substituted with quinone diazide, but on average, more than 40 mole percent of the total functional groups are substituted with quinone diazide. better. By containing such a quinonediazide compound, a resin composition sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of mercury lamps, which are common ultraviolet rays, can be obtained.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, BisP -EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P , BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-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 (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-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-Dimethicone Oxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetyloxymethyl-p-cresol, naphthol, tetrahydroxy di Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but is not limited to such.

Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylene, 4,4'-diaminodiphenyl ether, etc., but not limited for such.

Moreover, as a polyhydroxypolyamine-based compound, specifically, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, etc. are mentioned, but is not limited to such.

Among them, a quinonediazide compound containing a phenolic compound and an ester with a 4-naphthoquinonediazidesulfonyl group is preferable. Thereby, higher sensitivity and higher resolution for i-ray exposure can be obtained.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed part and the unexposed part can be obtained, and higher sensitivity can be achieved, which is preferable. Furthermore, a sensitizer etc. can be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also simply referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the following formula (OS-103), the formula (OS-104) or the formula (OS-105) The indicated oxime sulfonate compounds are preferred.

[chemical formula 40]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are a plurality of X ³ , they may be the same or different. The alkyl and alkoxy groups in ^X3 above may have substituents. As the alkyl group in the aforementioned ^X3 , a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in ^X3 above, a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned ^X3 , chlorine atom or fluorine atom is preferable. In formula (OS-1), m3 represents the integer of 0-3, 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different. In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, a halogenated alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons 5 is preferably a halogenated alkoxy group, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W, or an anthracenyl group which may be substituted by W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, a halogenated alkyl group with 1 to 5 carbons or a halogenated alkoxy group with 1 to 5 carbons , an aryl group having 6 to 20 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms.

In the formula (OS-1), m3 is 3, X ³ is a methyl group, the substitution position of X ³ is an ortho position, R ³⁴ is a linear alkyl group with 1 to 10 carbons, 7,7-dimethyl- 2-Oxonorylmethyl or p-tolyl compounds are particularly preferred.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include those described in paragraphs 0064 to 0068 of JP-A-2011-209692 and in paragraphs 0158-0167 of JP-A-2015-194674. The following compounds are described, and these contents are incorporated into this specification.

[chemical formula 41]

In the formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are multiple R ^s2 independently representing a hydrogen atom, an alkyl group, an aryl group or a halogen Atoms, sometimes there are a plurality of R ^s6 independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 Or 2, ms represents an integer from 0 to 6. In formula (OS-103) ~ formula (OS-105), R ^s1 represents the alkyl group (preferably 1-30 carbon number), aryl group (preferably 6-30 carbon number) or heteroaryl group ( (C4-30 are preferable) may have a known substituent within the range which can acquire the effect of this invention.

In formula (OS-103) to formula (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably with 1 to 12 carbons) or an aryl group (preferably with 6 to 30 carbons), A hydrogen atom or an alkyl group is more preferable. There are sometimes more than 2 R ^s2 in the compound, 1 or 2 are alkyl, aryl or halogen atom is better, 1 is alkyl, aryl or halogen atom is better, 1 is An alkyl group and the remainder being hydrogen atoms are particularly preferred. The alkyl group or aryl group represented by R ^s2 may have a known substituent as long as the effect of the present invention can be obtained. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulas (OS-103) to (OS-105), the ring including Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formula (OS-103) ~ formula (OS-105), ns represents 1 or 2, when Xs is O, ns is 1 is better, and when Xs is S, ns is 2 is better good. In the formula (OS-103) to the formula (OS-105), the alkyl group (preferably 1-30 carbon number) and alkoxy group (preferably 1-30 carbon number) represented by R ^s6 may have substituents . In Formula (OS-103) to Formula (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Also, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and the above formula (OS-104 ) represented by the compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The indicated compounds are particularly preferred. [chemical formula 42]

In the formula (OS-106) to the formula (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, R ^t8 represents a hydrogen atom, or an alkane with 1 to 8 carbons group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy, R ^t2 represents hydrogen atom or methyl. In the formula (OS-106) to the formula (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formula (OS-106) to formula (OS-111), R ^t8 represents a hydrogen atom, an alkyl group with 1 to 8 carbons, a halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbons, a halogen atom or a phenyl group, more preferably an alkyl group with 1 to 8 carbons, and even more preferably an alkyl group with 1 to 6 carbons , methyl is particularly preferred.

In the formula (OS-106) to the formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferred. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z) of the oxime may be any of them, or may be a mixture. Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and JP-A-2015-194674. Compounds described in paragraphs 0168 to 0194 of the publication, and these contents are incorporated into the present specification.

Other preferred aspects of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

[chemical formula 43]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acyl, carbamoyl, sulfamoyl, sulfo , cyano, aryl or heteroaryl. The aspect that R ^u9 is a cyano group or an aryl group is more preferable, and the aspect that R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferred. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 - , R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 ~ R ^u4 independently represent hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxycarbonyl, alkylcarbonyl , arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may undergo ring condensation to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, it is preferable that R ^u1 to R ^u4 are all hydrogen atoms. All of the above substituents may further have a substituent.

作為市售品，可以舉出WPAG-336（FUJIFILM Wako Pure Chemical Corporation製）、WPAG-443（FUJIFILM Wako Pure Chemical Corporation製）、MBZ-101（Midori Kagaku Co.,Ltd.製）等。 It is more preferable that the compound represented by the above-mentioned formula (OS-101) is a compound represented by the formula (OS-102). In addition, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or a mixture thereof. Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraphs 0102 to 0106 of JP-A-2011-209692 and in paragraphs 0195-0207 of JP-A-2015-194674, And compile these contents into this manual. Among the above-mentioned compounds, the following b-9, b-16, b-31 and b-33 are preferable. [chemical formula 44]

Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like.

Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [chemical formula 45]

Specific examples of organic halogenated compounds include Wakabayashi et al. "Bull Chem.Soc Japan" 42, 2924 (1969), US Pat. JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) etc., and these contents are incorporated into this specification. In particular, a trihalomethyl-substituted azole compound: S-trioxazole compound can be cited as a preferable example. More preferably, there can be mentioned s-three-one derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-three-one ring, specifically, for example, 2, 4, 6 -Tris(monochloromethyl)-s-tris-tris, 2,4,6-tris(dichloromethyl)-s-s-tris, 2,4,6-tris(trichloromethyl)-s-tris 𠯤, 2-methyl-4,6-bis(trichloromethyl)-s-tris-𠯤, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris-s-s, 2-( α,α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-trichloride, 2-phenyl-4,6-bis(trichloromethyl)-s-trichloride , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trichloromethyl, 2-(3,4-epoxyphenyl)-4,6-bis(trichloro Methyl)-s-trimethalone, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trimethoxyl, 2-[1-(p-methoxyphenyl)-2 ,4-butadienyl]-4,6-bis(trichloromethyl)-s-trimethanone, 2-styryl-4,6-bis(trichloromethyl)-s-trimethalone, 2 -(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-trichloromethyl, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) base)-s-three 𠯤, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three 𠯤, 2-(4-naphthyloxynaphthyl)-4,6-bis (Trichloromethyl)-s-trichloromethyl, 2-phenylthio-4,6-bis(trichloromethyl)-s-trichloromethyl, 2-benzylthio-4,6-bis(trichloromethyl base)-s-three 𠯤, 2,4,6-tris(dibromomethyl)-s-three 𠯤, 2,4,6-tris(tribromomethyl)-s-three 𠯤, 2-methyl -4,6-bis(tribromomethyl)-s-tribromomethyl, 2-methoxy-4,6-bis(tribromomethyl)-s-tribromomethyl, etc.

As an organic borate compound, for example, JP-A-62-143044, JP-A-62-150242, JP-9-188685, JP-9-188686, JP-A, Kaiping No. 9-188710, Japanese Patent Application No. 2000-131837, Japanese Patent Application No. 2002-107916, Japanese Patent Application No. 2764769, Japanese Patent Application No. 2002-116539 and Kunz, Martin "Rad Tech'98 Organoborates described in "Proceeding April 19-22, 1998, Chicago", etc., Japanese Patent Application Publication No. 6-157623, Japanese Patent Application Publication No. 6-175564, and Japanese Patent Application Publication No. 6-175561 Organoboronium complexes or organoboroxoconium complexes, Japanese Patent Application Laid-Open No. 6-175554, organoboronium complexes described in Japanese Patent Application Laid-Open No. 6-175553, Japanese Patent Application Laid-Open No. 9-188710 The organic boron phosphonium complexes described in the publication No. 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP Organoboron transition metal coordination complexes such as JP-A No. 7-292014 are given as specific examples, and the contents thereof are incorporated in the present specification.

Examples of the diazide compound include compounds described in JP-A-61-166544, JP-A-2001-132318, and diazo-diazo compounds.

Examples of the above-mentioned onium salt compounds include diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal et al, Polymer, 21,423 (1980), U.S. Patent No. 4,069,055 Ammonium salts described in Japanese Patent Application Laid-Open No. 4-365049, etc., phosphonium salts described in each of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, European Patent No. 104,143, and U.S. Patent No. 339,049 No., each description of U.S. Patent No. 410,201, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, EP No. 370,693, European Patent No. 390,214, and European Patent No. 233,567 No., European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Selenium salts described in J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047 (1979), C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct. (1988), arsenic salts, pyridinium salts and other onium salts, etc., and the contents of these are incorporated into this specification.

式（RI-I）中，Ar ₁₁表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數2～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基的碳數為6～20的芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₁₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar ₂₁、Ar ₂₂各自獨立地表示可以具有1～6個取代基的碳數1～20的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₂₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R ₃₁、R ₃₂、R ₃₃各自獨立地表示可以具有1～6個取代基之碳數6～20的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面考慮，芳基為較佳。作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數為1～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₃₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。 Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III). [chemical formula 46]

In the formula (RI-I), Ar ₁₁ represents an aryl group having 1 to 6 substituents with carbon number of 20 or less. Preferred substituents include alkyl groups with 1 to 12 carbon atoms, and alkyl groups with 2 carbon atoms. Alkenyl with 1 to 12 carbons, alkynyl with 2 to 12 carbons, aryl with 6 to 12 carbons, alkoxy with 1 to 12 carbons, aryloxy with 1 to 12 carbons, halogen atom, 1 carbon Alkylamino group with ~12 carbons, dialkylamino group with 2 to 12 carbons, alkylamide group with 1 to 12 carbons in the alkyl group or arylamide with 6 to 20 carbons in the aryl group group, carbonyl, carboxyl, cyano, sulfonyl, thioalkyl with 1 to 12 carbons, and thioaryl with 1 to 12 carbons. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, from In terms of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents. Preferred substituents include 1 to 12 carbon atoms. Alkyl, alkenyl with 2 to 12 carbons, alkynyl with 2 to 12 carbons, aryl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, aryloxy with 1 to 12 carbons , a halogen atom, a monoalkylamino group with 1 to 12 carbon atoms, a dialkylamino group with an alkyl group with 1 to 12 carbon atoms, an alkylamido group with an alkyl group with 1 to 12 carbon atoms Or an arylamido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbons, or a thioaryl group having 1 to 12 carbons. Z ₂₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, from In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group with 1 to 6 substituents and a carbon number of 6 to 20, preferably , from the viewpoint of reactivity and stability, aryl is preferred. Preferred substituents include alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, alkynyl groups having 2 to 12 carbons, aryl groups having 1 to 12 carbons, and aryl groups having 1 to 12 carbons. 12 alkoxy, aryloxy with 1 to 12 carbons, halogen atom, monoalkylamino with 1 to 12 carbons, dialkylamino with 1 to 12 carbons in the alkyl, alkyl Alkylamido or arylamido with 1 to 12 carbons, carbonyl, carboxyl, cyano, sulfonyl, thioalkyl with 1 to 12 carbons, thioaryl with 1 to 12 carbons base. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, from In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

[化學式48]

[化學式49]

[化學式50]

上述式中，Rf表示全氟烷基。 Specific examples of a preferable photoacid generator include the following. [chemical formula 47]

[chemical formula 48]

[chemical formula 49]

[chemical formula 50]

In the above formula, Rf represents a perfluoroalkyl group.

The photoacid generator is preferably used at 0.1 to 20% by mass, more preferably at 0.5 to 18% by mass, more preferably at 0.5 to 10% by mass, and at 0.5 to 3% by mass relative to the total solid content of the resin composition. It is still more preferable to use 0.5-1.2 mass %, and it is still more preferable. A photoacid generator may be used individually by 1 type, and may use it in combination of plural types. When using plural types in combination, the total amount is preferably within the above range. Moreover, in order to provide photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.

<Base generator> The resin composition of this invention may contain a base generator. Among them, the base generator is a compound capable of generating base through physical or chemical action. As a preferable base generator for the resin composition of this invention, a thermal base generator and a photobase generator are mentioned. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. By adding a thermal base generator to the resin composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the mechanical properties and chemical resistance of the cured product are good. For example, it can be used as a rewiring layer included in a semiconductor package. The performance with the interlayer insulating film becomes good. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamic acid compounds, etc. Ester compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amidoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amidoimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. As a specific compound of a nonionic base generating agent, the compound represented by formula (B1), formula (B2), or formula (B3) is mentioned. [chemical formula 51]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Moreover, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-type carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited thereto.

In formula (B1) and formula (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably has a cyclic structure, and at least two of them have a cyclic structure. The ring structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1-24 carbons, more preferably 2-18, more preferably 3-12), alkenyl (2-24 carbons is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (6-22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred) or arane A group (preferably 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms) is preferred. These groups may have substituents within the range in which the effects of the present invention are exerted. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the formed ring, a nitrogen-containing heterocyclic ring with 4 to 7 members is preferable. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbons, more preferably 2 to 18, and more preferably 3 to 12) as Preferably, a cycloalkyl group that may have a substituent (preferably 3 to 24 carbons, more preferably 3 to 18, and even more preferably 3 to 12) is more preferred, and a cyclohexyl group that may have a substituent is further preferred. good.

Examples of Rb ³ include alkyl (preferably 1-24 carbons, more preferably 2-18, still more preferably 3-12), aryl (preferably 6-22 carbons, 6-18 is more preferred, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl group (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), aralkenyl (8-24 carbons is preferred, 8-20 is more preferred, 8-16 is further preferred), alkane Oxygen (preferably 1-24 carbons, more preferably 2-18, further preferably 3-12), aryloxy (preferably 6-22 carbons, more preferably 6-18, 6-18 12 is further preferred) or aralkoxy group (with 7 to 23 carbons is preferred, 7 to 19 is more preferred, 7 to 12 is further preferred). Among them, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and still more preferably having 3 to 12 carbon atoms), aralkenyl groups and aralkoxy groups are preferred. Rb ³ may have a substituent as long as the effect of the present invention is exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [chemical formula 52]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in the formula (B1), respectively. Rb ¹³ is alkyl (preferably 1-24 carbons, more preferably 2-18, further preferably 3-12), alkenyl (preferably 2-24 carbons, more preferably 2-18, 3-12 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 are more preferable, 7-12 are still more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb ¹³ is preferably an aralkyl group.

Rb ³³ and Rb ³⁴ are independently a hydrogen atom, an alkyl group (preferably 1-12 carbons, more preferably 1-8, more preferably 1-3), alkenyl (2-12 carbons are relatively preferably, 2-8 is more preferred, 2-3 is further preferred), aryl (6-22 carbons is preferred, 6-18 is preferred, 6-10 is further preferred), aralkyl ( Carbon number 7-23 is preferable, 7-19 is more preferable, 7-11 is still more preferable), hydrogen atom is more preferable.

Rb ³⁵ is alkyl (preferably 1-24 carbons, more preferably 1-12, further preferably 3-8), alkenyl (preferably 2-12 carbons, more preferably 2-10, 3-8 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 is more preferable, 7-12 is still more preferable), and aryl group is more preferable.

Moreover, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [chemical formula 53]

Rb ¹¹ and Rb ¹² have the same meaning as Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atom, alkyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbons, 2 ～6 is more preferred, 2～3 is further preferred), aryl group (carbon number 6～22 is preferred, 6～18 is more preferred, 6～10 is further preferred), aralkyl group (carbon number 7 ～23 is preferred, 7～19 is more preferred, 7～11 is further preferred), hydrogen atom or methyl group are preferred. Rb ¹⁷ is alkyl (preferably 1-24 carbons, more preferably 1-12, further preferably 3-8), alkenyl (preferably 2-12 carbons, more preferably 2-10, 3-8 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7 to 19 are more preferred, and 7 to 12 are further preferred), among which aryl is preferred.

[chemical formula 54]

In the formula (B3), L represents a hydrocarbon group, which is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the connecting chain path is 3 more than one. In addition, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, "connecting chain" refers to the atom chain on the path between two atoms or connecting atom groups connecting the connecting objects in the shortest way (minimum number of atoms) connecting the connecting objects. For example, in the compound represented by the following formula, L is composed of phenylene ethylenyl, and has ethylenyl as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (that is, is The number of atoms constituting the connecting chain, hereinafter also referred to as "the length of the connecting chain" or "the length of the connecting chain".) is 4. [chemical formula 55]

It is preferable that the number of carbons (including carbon atoms other than the carbon atoms in the linking chain) in L in the formula (B3) is 3-24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly advancing the intramolecular cyclization reaction. In particular, the linking chain length of L is preferably 4 or 5, and 4 is most optimal. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416, and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

Moreover, it is also preferable that a base generator contains the compound represented by following formula (N1). [chemical formula 56]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The connecting chain length of the linking group is preferably 1 or more, and more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is still more preferable. The linking chain length is the number of atoms present in the arrangement of atoms that forms the shortest path between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 independently represent a monovalent organic group (preferably 1-24 carbons, more preferably 2-18, more preferably 3-12), hydrocarbon group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 10 is further preferred) is preferred, specifically, aliphatic hydrocarbon groups (preferably 1 to 24 carbons, 1 to 12 are preferred) More preferably, 1 to 10 are more preferably) or aromatic hydrocarbon groups (6 to 22 carbons are more preferred, 6 to 18 are more preferred, 6 to 10 are further preferred), and aliphatic hydrocarbon groups are preferred. It is preferable to use an aliphatic hydrocarbon group as R ^N1 and R ^N2 because the basicity of the generated base is high. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

Examples of the aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, chain alkyl groups, and chain alkyl groups. An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms. Regarding linear or branched chain alkyl groups, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third pentyl, isohexyl, etc. The cyclic alkyl group is preferably one with 3-12 carbon atoms, more preferably 3-6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The group related to the combination of a chain alkyl group and a cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and still more preferably 4 to 12 carbon atoms. Groups related to the combination of chain alkyl and cyclic alkyl include, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. Among them, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbons from the viewpoint of raising the boiling point of a base decomposed to be described later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in formulations that place emphasis on the adhesiveness of the laminated layer with a metal (for example, copper).

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When forming a ring structure, an oxygen atom etc. may exist in a chain. Also, the ring structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, but a single ring is preferable. As the formed ring structure, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferable, for example, pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring , imidazolidine ring, pyrazolidine ring, piperidine ring, piperidine ring, morpholine ring, etc., preferably pyrroline ring, pyrrolidine ring, piperidine ring, piperridine ring, and morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group decomposed by the action of an acid or a base is preferable, and a protecting group decomposed by an acid is preferable.

Specific examples of the protecting group include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain. A methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned as a chain-like or cyclic alkyl group. The chain-like alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methoxymethyl (MOM) group, an ethoxyethyl ( EE) base etc. Examples of the cyclic alkyl group having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl (THP) group, and the like.

The divalent linking group constituting L is not particularly defined, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferable, a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a divalent hydrocarbon group that may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is still more preferable. These groups preferably do not have an oxygen atom. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group has preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms, and still more preferably 6-10 carbon atoms. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) is preferably a carbon number of 7 to 22, more preferably 7 to 18, and 7 to 10 for further improvement.

As the linking group L, specifically, a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylylene group, and an arylylene group are preferable. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The cyclic alkylene group has preferably 3-12 carbon atoms, more preferably 3-6 carbon atoms. The group related to the combination of a chain alkylene group and a cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and still more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be straight or branched. The alkylene group having an oxygen atom in the chain has preferably 1-12 carbon atoms, more preferably 1-6 carbon atoms, and still more preferably 1-3 carbon atoms.

The linear or branched alkenylene group has preferably 2-12 carbon atoms, more preferably 2-6 carbon atoms, and still more preferably 2-3 carbon atoms. The number of C=C bonds in the linear or branched alkenylene group is preferably 1-10, more preferably 1-6, and still more preferably 1-3. The cyclic alkenylene group preferably has 3-12 carbon atoms, more preferably 3-6 carbon atoms. The number of C=C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, and still more preferably 1-2. The arylylene group has preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms, and still more preferably 6-10 carbon atoms. The arylalkylene group preferably has 7-23 carbon atoms, more preferably 7-19 carbon atoms, and still more preferably 7-11 carbon atoms. Among them, chain alkylene, cyclic alkylene, alkylene having an oxygen atom in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -Ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), vinylene Phenyl (1,2-phenylene), phenylene methylene (especially 1,2-phenylene methylene), oxyethylene (especially 1,2-vinyloxy-1,2- Ethyl) is more preferred.

As the base generating agent, the following examples can be mentioned, but the present invention is not limitedly interpreted by these.

[chemical formula 57]

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited thereto. [chemical formula 58]

Specific examples of imide salts include the following compounds, but the present invention is not limited thereto. [chemical formula 59]

When the resin composition of this invention contains a base generator, it is preferable that content of a base generator is 0.1-50 mass parts with respect to 100 mass parts of resins in the resin composition of this invention. The lower limit is more preferably at least 0.3 parts by mass, and more preferably at least 0.5 parts by mass. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, and may be 4 parts by mass or less. The base generator can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that a total amount exists in the said range.

<Solvent> It is preferable that the resin composition of the present invention contains a solvent. As the solvent, known solvents can be used arbitrarily. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, alkanes Ethyl oxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., 2-alkoxy Methyl oxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkane Ethyl oxy-2-methylpropionate (for example, 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, ethyl hexanoate, ethyl heptanoate , dimethyl malonate, diethyl malonate, etc. are preferred.

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levodextranone, dihydrodextran Sugar ketone and the like are preferred.

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferred.

As the arsonites, for example, dimethyl arsonite is preferred.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylethyl Amide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylacrylamide, N-formylmorpholine, N-acetylmorpholine, etc. are preferred.

Ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like as preferred ones.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methanol, Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monodiethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl Ether, methyl phenyl carbinol, n-pentanol, methyl pentanol and diacetone alcohol, etc.

Regarding the solvent, it is also preferable to mix two or more kinds from the viewpoint of improving the properties of the coated surface.

In the present invention, selected from methyl 3-ethoxy propionate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Esters, Methyl 3-Methoxypropionate, 2-Heptanone, Cyclohexanone, Cyclopentanone, γ-Butyrolactone, Dimethylsulfene, Ethyl Carbitol Acetate, Butyl Carbitol One solvent or a combination of two or more of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucose ketone, and dihydroglucose ketone A mixed solvent is preferred. It is particularly preferable to use dimethylsulfoxide and γ-butyrolactone or N-methyl-2-pyrrolidone and ethyl lactate simultaneously.

From the viewpoint of applicability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass, of the total solid content concentration of the resin composition of the present invention. , It is still more preferable to set it as the quantity of 10-70 mass %, and it is still more preferable to set it as 20-70 mass %. As for the solvent content, it may be adjusted according to the desired thickness of the coating film and the coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types. When two or more solvents are contained, it is preferable that the total is within the above-mentioned range.

＜Metal Adhesion Improver＞ It is preferable that the resin composition of the present invention contains a metal adhesion improving agent for improving adhesion with metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesive additives, titanium-based adhesive additives, compounds having a sulfonamide structure, compounds containing thiourea, phosphoric acid derivatives Compounds, β-ketoester compounds, amino compounds, etc.

〔Silane coupling agent〕 Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in International Publication No. 2011/080992 Compounds described in paragraphs 0063 to 0071 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[chemical formula 60]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxy 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyl Triethoxysilane, p-Styryltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔Aluminum-based adhesive agent〕 Examples of the aluminum-based adhesive agent include aluminum tris(acetylacetonate)aluminum, tris(acetylacetonate)aluminum, aluminum ethylacetate diisopropoxide, and the like.

In addition, as other metal adhesion improving agents, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and vulcanized compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used. system compounds, and these contents are compiled into this specification.

The content of the metal adhesion improving agent is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin . By setting it as more than the said lower limit, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as below the said upper limit, the heat resistance of a pattern, and a mechanical characteristic become favorable. The metal adhesiveness improving agent may be only 1 type, and may be 2 or more types. When using 2 or more types, it is preferable that the total is within the said range.

＜Migration Inhibitor＞ It is preferable that the resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the transfer of metal ions originating in the metal layer (metal wiring) into the film can be effectively suppressed.

The migration inhibitor is not particularly limited, but examples include Tetrazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, three pyran ring) compounds, with Thiourea and mercapto compounds, hindered phenolic compounds, salicylic acid derivatives, hydrazide derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

Alternatively, an ion trapping agent that traps anions such as halogen ions can also be used.

As other migration inhibitors, rust inhibitors described in paragraph 0094 of JP 2013-015701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, JP 2011 - Compounds described in paragraph 0052 of Japanese Patent Laid-Open No. 059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015/199219 Compounds, etc., and these contents are incorporated into this specification.

Specific examples of migration inhibitors include the following compounds.

[chemical formula 61]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total solid content of the resin composition of the present invention. , 0.1 to 1.0% by mass is still more preferable.

The migration inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of migration inhibitors, the total of them is preferably within the above range.

＜Polymerization inhibitor＞ It is preferable that the resin composition of the present invention contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, etc. .

As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol are preferably used , gallicol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butyl phenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-benzene Hydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2 ,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3, 5-(tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(alpha) -2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetra Methyl piperidine 1-oxyl radical, phenothiazine, phenanthrene, 1,1-diphenyl-2-pyrrole hydrazine, dibutyl copper dithiocarbonate (II), nitrobenzene, N- Nitro-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2 ]-non-2-ene-N,N-dicarbonyl), etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the content is incorporated in this specification. .

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20% by mass, more preferably 0.02 to 15% by mass relative to the total solid content of the resin composition of the present invention, 0.05-10 mass % is still more preferable.

The polymerization inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of polymerization inhibitors, the total is preferably within the above range.

＜Acid Scavenger＞ It is preferable that the resin composition of the present invention contains an acid scavenger in order to reduce performance changes due to time from exposure to heating. Among them, the acid-scavenging agent refers to a compound capable of capturing acid generation by existing in the system, and a compound with low acidity and high pKa is preferable. As an acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amide, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts More preferably, secondary amines, tertiary amines, and ammonium salts are more preferred. As the acid scavenger, preferably, a compound having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, aniline structure or a pyridine structure, and an alkylamine derivative having a hydroxyl group and/or an ether bond substances, aniline derivatives with hydroxyl and/or ether linkages, etc. In the case of having an onium structure, the acid scavenger is one having a cation selected from among ammonium, diazo, iodonium, permeum, phosphonium, pyridinium, etc. and an anion of an acid having a lower acidity than the acid generated by the acid generator. Salt is preferred.

Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, and the like. Examples of acid-scavenging agents having a diazabicyclic structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triaryl perium hydroxide, benzoylmethyl percited hydroxide, permeic hydroxide having a 2-oxoalkyl group, specifically Triphenylmalladium hydroxide, tri(tert-butylphenyl)malladium hydroxide, bis(tertiary-butylphenyl)iodonium hydroxide, benzoylmethylthiophenium hydroxide, 2-oxopropane hydroxide base thienium etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid-scavenging agent which has a trialkylamine structure. Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, and the like. Pyridine, 4-picoline, etc. are mentioned as an acid-scavenging agent which has a pyridine structure. Examples of the alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline and the like.

Specific examples of preferred acid scavenger include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, Cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine , DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenedi Amine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine Amine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, refined triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine , methyl piperidine, piper 𠯤, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylene Diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidinium, pyrazole, pyrazoline, aminomorpholine, aminoalkylomorpholine, etc.

These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is based on the total solid content of the composition, usually 0.001 to 10% by mass. Preferably, it is 0.01 to 5% by mass.

The use ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio) = 2.5-300. That is, from the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution due to the thickness of the relief pattern with time from exposure to heat treatment , below 300 is better. The acid generator/acid scavenger (molar ratio) is more preferably from 5.0 to 200, further preferably from 7.0 to 150.

＜Other additives＞ The resin composition of the present invention can contain various additives, such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, antioxidants, etc. Coagulants, phenolic compounds, other polymer compounds, plasticizers and other additives (such as defoamers, flame retardants, etc.), etc. Properties such as film physical properties can be adjusted by appropriately containing these components. Regarding these components, for example, reference can be made to the description in paragraph 0183 and later of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812 specification) and the description in Japanese Patent Application Publication No. 2008-250074 0101 to 0104, 0107 to 0109, etc., and incorporate these contents into this specification. When compounding these additives, it is preferable to make the total compounding quantity into 3 mass % or less of the solid content of the resin composition of this invention.

〔Surfactant〕 As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the resin composition of the present invention, the liquid properties (in particular, fluidity) when prepared as a coating liquid are further improved, thereby further improving the uniformity of the coating thickness and the liquid-saving property. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced to improve wettability to the surface to be coated, thereby Improves coatability on the surface to be coated. Therefore, it is possible to more preferably form a film having a uniform thickness with less thickness unevenness.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (the above are ASAHI GLASS CO.,LTD. ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used. The content is incorporated into this manual. A block polymer can also be used as the fluorine-based surfactant. Specific examples thereof include compounds described in JP-A-2011-89090, and the contents thereof are incorporated in the present specification. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds, which contain repeating units derived from (meth)acrylate compounds having fluorine atoms and derived from 2 or more (preferably It is a repeating unit of (meth)acrylate compound of alkyleneoxy group (preferably ethyleneoxy group, propyleneoxy group) of 5 or more, and the following compounds can also be exemplified as the fluorine-based interface used in the present invention active agent. [chemical formula 62]

The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000. Fluorinated Surfactant A fluorinated polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorinated surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, and the contents thereof are incorporated in the present specification. Moreover, as a commercial item, DIC CORPORATION Megaface RS-101, RS-102, RS-718K etc. are mentioned, for example.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid-saving properties, and its solubility in the composition is also good.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc. above), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co. ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D -6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO., LTD.), etc.

As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerin propoxylate, glycerin ethoxylate etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate Esters, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co. Ltd.), and the like.

Surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

〔Higher fatty acid derivatives〕 In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention, so that it will be uneven in the drying process after coating. exist on the surface of the resin composition of the present invention.

Moreover, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used as a higher fatty acid derivative, and this content is incorporated in this specification.

When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be only 1 type, or may be 2 or more types. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total thereof is within the above-mentioned range.

〔Inorganic particles〕 The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

The average particle diameter of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, still more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The said average particle diameter of an inorganic particle is a primary particle diameter, and is a volume average particle diameter. The volume average particle diameter can be measured by the dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When it is difficult to perform the above measurement, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

〔UV absorber〕 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfone-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc., as benzophenone-based ultraviolet absorbers. Examples of agents include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl Methanone etc. Also, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3'-tert-amyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3',5'-di-tert-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetra Methyl) phenyl] benzotriazole, etc.

Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, etc. . Furthermore, as an example of a trioxane-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -Bis(2,4-dimethylphenyl)-1,3,5-trimethalone, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethanone, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-trimethanone and other mono(hydroxyphenyl)trimethanone compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-trimethylphenyl, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-trimethanone, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(hydroxyphenyl)tris(2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-di Butoxyphenyl)-1,3,5-trimethanone, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-trimethanium, 2,4, 6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-trisanthene and other tris(hydroxyphenyl)trisanthene compounds, etc.

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001% by mass or more and 1% by mass relative to the total solid content of the composition of the present invention. It is preferably at most mass %, more preferably at least 0.01 mass % and at most 0.1 mass %.

〔Organotitanium compound〕 The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, it is possible to form a resin layer excellent in chemical resistance even when it is cured at a low temperature.

Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the resin composition has excellent storage stability and can obtain a good hardening pattern, so a titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are bis(triethanolamine)titanium diisopropoxide, bis(n-butanol)bis(2,4-pentanedione)titanium, bis(2,4-pentanedione)titanium diisopropoxide, Bis(tetramethylheptanedionate)titanium isopropanol, bis(acetylacetate)titanium diisopropanol, etc. II) Titanium tetraalkoxide compound: such as titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexyloxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearate, tetrakis[bis{2,2-(allyloxy Methyl) butanol}] titanium and so on. III) Titanocene compounds: e.g. pentamethylcyclopentadienyl trimethoxide titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxide compound: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenylsulfonate) isopropoxide, and the like. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), titanium oxide phthalocyanine, and the like. VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the organotitanium compound is selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds and III) titanocene compounds from the viewpoint of exhibiting better chemical resistance. At least one compound is preferred. In particular, bis(acetylacetate)titanium diisopropoxide, tetra(n-butoxide)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro- 3-(1H-Pyrrol-1-yl)phenyl)titanium is preferred.

When compounding an organic titanium compound, the compounding quantity is 0.05-10 mass parts with respect to 100 mass parts of specific resins, More preferably, it is 0.1-2 mass parts. When the compounding amount is 0.05 mass parts or more, the obtained hardened pattern more effectively exhibits good heat resistance and chemical resistance. On the other hand, when the compounding amount is 10 mass parts or less, the composition Storage stability is more excellent.

〔Antioxidants〕 The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, the elongation characteristic of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenolic compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Moreover, it is also preferable that an antioxidant is a compound which has a phenol group and a phosphite group in the same molecule. Moreover, phosphorus antioxidant can also be used preferably as an antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphine-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]dioxaphosphine-2-yl)oxy]ethyl]amine and ethylphosphite bis(2,4-di-tert-butyl-6-methyl phenyl) etc. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO- 80 and Adekastab AO-330 (the above are manufactured by ADEKA CORPORATION), etc. Moreover, the compound described in paragraph 0023-0048 of Japanese Patent No. 6268967 can also be used as an antioxidant, and the content is incorporated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As a potential antioxidant, there can be mentioned a compound in which the part that exerts an antioxidant effect is protected by a protecting group, and is heated at 100 to 250°C or carried out at 80 to 200°C in the presence of an acid/alkali catalyst. A compound that acts as an antioxidant by detaching the protecting group by heating. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Laid-Open No. 2017-008219, and the contents thereof are incorporated in this specification. As a commercial item of a latent antioxidant, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) etc. are mentioned. As examples of preferred antioxidants, 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and formula (3) The indicated compound.

[chemical formula 63]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group with 2 or more carbons (preferably 2 to 10 carbons), and R ⁶ represents an alkyl group with 2 or more carbons (preferably 2 to 10 carbons). alkyl. R ⁷ represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and a 1 to 4 valent organic group including at least one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

The compound represented by formula (3) suppresses the oxidation degradation of the aliphatic group and phenolic hydroxyl group which resin has. In addition, metal oxidation can be suppressed by the antirust effect on metal materials.

It can act on both resin and metal materials, so k is an integer of 2-4 more preferably. Examples of R ⁷ include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl A group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc. may have a substituent. Among them, it is preferable to have an alkyl ether group and -NH- from the viewpoint of solubility in a developer and metal adhesion, and from the viewpoint of interaction with resin and metal adhesion when forming a metal complex Consider, -NH- is more preferred.

Examples of the compound represented by the general formula (3) include the following, but are not limited to the following structures.

[chemical formula 64]

[chemical formula 65]

[chemical formula 66]

[chemical formula 67]

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By setting the addition amount to 0.1 mass parts or more, even in a high-temperature and high-humidity environment, it is easy to obtain the effect of improving elongation characteristics or adhesion to metal materials, and by setting the addition amount to 10 mass parts or less, for example The sensitivity of the resin composition is improved by interacting with the photosensitizer. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that these total amounts are in the said range.

〔Anti-coagulation agent〕 The resin composition of this embodiment may contain an anti-agglomeration agent as needed. Sodium polyacrylate etc. are mentioned as an anti-agglomeration agent.

In the present invention, the anti-aggregating agent may be used alone or in combination of two or more. The composition of the present invention may or may not contain an anti-aggregating agent, but when included, the content of the anti-aggregating agent is 0.01% by mass or more and 10% by mass relative to the total solid content of the composition of the present invention. It is preferably at most mass %, more preferably at least 0.02 mass % and at most 5 mass %.

〔Phenolic compounds〕 The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

In the present invention, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% by mass relative to the total solid content of the composition of the present invention. It is preferably at most mass %, more preferably at least 0.02 mass % and at most 20 mass %.

〔Other polymer compounds〕 Examples of other polymer compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers of these things etc. Other high molecular compounds may be modified bodies introduced with cross-linking groups such as methylol, alkoxymethyl, and epoxy groups.

In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds, but in the case of inclusion, the content of other polymer compounds is 0.01% by mass relative to the total solid content of the composition of the present invention More than 30 mass % is more preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000mm ² /s to 12,000mm ² /s is preferable, 2,000mm ² /s to 10,000mm ² /s is more preferable, and 2,500mm ² /s to 8,000mm ² /s is more preferable for further improvement. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. If it is 1,000 mm ² /s or more, it is easy to coat with a film thickness required as an insulating film for rewiring, for example, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface morphology can be obtained.

<Restrictions on substances contained in resin compositions> The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and still more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition will be improved. As a method of maintaining the water content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container during storage, and the like can be mentioned.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and less than 0.5 mass ppm for further improvement. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.

Also, as a method for reducing the metal impurities accidentally included in the resin composition of the present invention, the following methods can be mentioned: selecting a raw material with a low metal content as the raw material constituting the resin composition of the present invention; The raw material of the product is filtered through a filter; polytetrafluoroethylene is lined in the device to carry out distillation under the condition of suppressing pollution as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm for further improvement. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above-mentioned ranges. As a method of adjusting the content of a halogen atom, ion exchange treatment etc. are mentioned preferably.

As a container for the resin composition of the present invention, a conventionally known container can be used. Also, as a storage container, in order to prevent impurities from being mixed into the raw material or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is composed of 6 types of 6-layer resins, or a bottle in which 6 types of resins are formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, proportions, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

<Synthesis Example 1: Synthesis of Polymer P-1> Put 49g (0.4 moles) of 2,4-dimethylphenol, 173g (1.6 moles) of m-cresol, and 130g ( 1.6 mol), 12.6 g (0.1 mol) of oxalic acid dihydrate, and 550 g of methyl isobutyl ketone were kept at a temperature of 90 to 100° C. and reacted for 8 hours while stirring. After washing this solution twice with 500 g of ion-exchanged water, 600 g of n-hexane was added, stirred for 30 minutes, and left still for 1 hour. Thereafter, the supernatant of the precipitated resin layer was removed by decantation. The obtained resin layer was concentrated, dehydrated, and dried to obtain a resin having a Mw of 8000 (polymer P-1).

<Synthesis Example 2: Synthesis of Polymer P-2> 7.76 g (25 millimoles) of 4,4'-oxydiphthalic dianhydride (ODPA) and 3,3',4,4'-linked 6.23 g (25 millimoles) of benzene tetracarboxylic dianhydride was added to the reaction container, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. While stirring at room temperature, 7.91 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction ended, it was cooled to room temperature and further left to stand for 16 hours. Next, under ice cooling, a solution obtained by dissolving 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. middle. Next, a suspension obtained by suspending 9.3 g (46 millimoles) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Furthermore, after stirring at room temperature for 2 hours, 3 ml of ethanol was added and stirred for 1 hour. Thereafter, 100 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate consisting of a crude polymer. The generated crude polymer was collected by filtration and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum-dried to obtain powdery polymer P-2. The weight average molecular weight (Mw) of this polymer was measured and found to be 23,000. Polymer P-2 is a resin having the following structure. The subscripts in parentheses indicate the molar ratio of each repeating unit. [chemical formula 68]

<Synthesis Example 3: Synthesis of Polymer P-3> 20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (obtained by drying at 140° C. for 12 hours), 16.8 g ( 129 millimoles) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 millimoles) of pyridine and 100 g of diglyme, and stirred at a temperature of 60 ° C for 18 hours, thereby producing a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled and 16.12 g (135.5 mmol) of SOCl2 were added over ₂ hours. Next, a solution obtained by dissolving 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C Meanwhile, it was added dropwise to the reaction mixture over 2 hours. After allowing the reaction mixture to react at 0° C. for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried for 2 days under reduced pressure. The weight average molecular weight of this polyimide precursor (polymer P-3) was 29,000. Polymer P-3 is a resin having the following structure. [chemical formula 69]

<Synthesis Example 4: Synthesis of Polymer P-4> 20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (obtained by drying at 140° C. for 12 hours), 16.8 g ( 129 millimoles) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 millimoles) of pyridine and 100 g of diglyme, and stirred at a temperature of 60 ° C for 18 hours, thereby producing a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester with SOCl ₂ , in the same manner as in Synthesis Example 3, a solution obtained by dissolving 4,4'-diaminodiphenyl ether in N-methylpyrrolidone It was added dropwise to the reaction mixture, after which the obtained reaction mixture was purified and dried. The weight average molecular weight of this polyimide precursor (polymer P-4) was 18,000. Polymer P-4 is a resin having the following structure. [chemical formula 70]

<Synthesis Example 5: Synthesis of Polymer P-5> Under dry nitrogen flow, 88.64 g (180 millimoles) of dicarboxylic acid diester formed from 4,4'-dicarboxydiphenyl ether and 1-hydroxybenzotriazole, 2,2-bis(3-amine 65.93g (180mmol) of hexafluoropropane, 12.00g (20mmol) of ED-600 (product name, manufactured by HUNTSMAN Co., Ltd.), and 800g of NMP were reacted at 25°C for 30 minutes, followed by Heating was performed in an oil bath, and the reaction was carried out at 80° C. for 8 hours. Next, 12.31 g (75 millimoles) of 5-norcamphene-2,3-dicarboxylic acid anhydride was added as a terminal blocking agent, and it stirred at 80 degreeC for 3 more hours, and completed reaction. After the reaction was completed, the solution was cooled to room temperature, the reaction mixture was filtered, and the reaction mixture was poured into 2 L of a mixed solution of water/isopropanol=3/1 (volume ratio) to obtain a precipitate. The precipitate was collected by filtration, washed with water three times, and then dried using a vacuum dryer at 80° C. for 20 hours to obtain polymer P-5 (polybenzoxazole precursor). The weight average molecular weight was 28,000.

Each composition was obtained by mixing the components described in the following table|surface. Concretely, the content of the components described in the table was the quantity (parts by mass) described in the table. In addition, in the table, the description of "-" shows that a composition does not contain a corresponding component.

[Table 1] Composition 1 2 3 4 5 6 7 8 9 10 resin P-1 40 40.6 - - - - - 37 - - P-2 - - - 35 - - - - - - P-3 - - - - 33.42 - - - - - P-4 - - - - - 36.79 - - 30 30 P-5 - - - - - - 32.86 - - - P-6 - - 47 - - - - - - - polymeric compound B-1 - - - 4 - - - - - - B-2 - - - - 5.01 - - - - - B-3 - 6 - - - - - - - - B-4 - - - - - - 3.29 - - - B-5 - - - - - - 1.64 - - - B-6 - - - - 6.69 5.53 6.57 - 6.2 6.2 B-7 - - 2.5 - - - - - - - B-8 - - - - - - - - - - B-9 - - - - - - - - - - B-10 - - - - - - - - - - polymerization initiator C-1 - - - - - - 1.31 - - - C-2 - - - - 0.17 - - - - - C-3 - - - - - 1.29 - - - - C-4 - - 0.5 1.31 - - - - - - C-5 - - - - 1.34 - - - - - C-6 - - - - - - - 5 - - C-7 - - - 1.4 - - - - - - C-8 - - - - - - - - 0.8 - C-9 - - - - - - - - 1.2 2.8 C-10 - - - - - - - - - - metal adhesion improver D-1 - - - - - - 1.58 - - - D-2 - - - - 1 - - - - - D-3 - - - - - 0.73 - - 0.5 0.5 D-4 - - - 0.7 - - - - - - D-5 - - - - - - - - - - migration inhibitor E-1 - - - 0.01 0.33 0.12 0.07 - 0.07 0.07 polymerization inhibitor F-1 - - - 0.1 - 0.1 0.1 - 0.05 0.05 F-2 - - - - 0.1 - - - - - F-3 - - - - - - - - - - F-4 - - - - - - - - - - Surfactant G-1 - - - - - - 0.1 - - - G-2 0.03 0.03 0.05 - - - - 0.03 - - base generator H-1 - - - - - 1.03 - - 0.8 0.8 additive I-1 - 0.4 - - - - - - - - I-2 - - - - 0.14 - - - - - I-3 - - - 2.4 - - - - - - I-4 - - - 1 - - - - - - I-5 12 - - - - - - 10 - - solvent J-1 - - - - - 43.53 52.48 - 48.38 47.58 J-2 - - - - - 10.88 - - 12 12 J-3 47.97 52.97 - 11.5 - - - 47.97 - - J-4 - - - 42.58 51.8 - - - - - J-5 - - 49.95 - - - - - - -

[Table 2] Composition 11 12 13 14 15 16 17 resin P-1 - - - - - - - P-2 - - - - - - - P-3 - - - - - - - P-4 30 31.5 28 18.5 9.5 - 9.5 P-5 - - - - - - - P-6 - - - - - - - polymeric compound B-1 - - - - - - - B-2 - - - - - - - B-3 - - - - - - - B-4 - - - - - - - B-5 - - - - - - - B-6 6.2 1.58 4.36 - - - - B-7 - - - - - - - B-8 - 4.73 - - - - - B-9 - - - 9 18 27.98 - B-10 - - - - - - 18 polymerization initiator C-1 - - 1.02 - - - - C-2 - - - - - - - C-3 - 2.21 - - - - - C-4 - - - - - - - C-5 - - - - - - - C-6 - - - - - - - C-7 - - - - - - - C-8 - - - - - - - C-9 - - - - - - - C-10 2.2 - - 1.8 1.8 1.8 1.8 metal adhesion improver D-1 - - - - - - - D-2 - - - - - - - D-3 0.5 0.63 0.58 - - - - D-4 - - - - - - - D-5 - - - 0.54 0.54 0.54 0.54 migration inhibitor E-1 0.07 0.1 0.1 0.12 0.12 0.12 0.12 polymerization inhibitor F-1 0.05 - - 0.06 0.06 0.06 0.06 F-2 - - - - - - - F-3 - 0.025 0.04 - - - - F-4 - 0.065 - - - - - Surfactant G-1 - - - - - - - G-2 - - - - - - - base generator H-1 0.8 0.88 1.05 - - - - additive I-1 - - - - - - - I-2 - - - - - - - I-3 - - - - - - - I-4 - - - - - - - I-5 - - - - - - - solvent J-1 48.18 46.63 51.89 55.98 55.98 55.98 55.98 J-2 12 11.65 12.97 14 14 14 14 J-3 - - - - - - - J-4 - - - - - - - J-5 - - - - - - -

The details of the abbreviations listed in the table are as follows. [resin] P-1～P-5: P-1～P-5 synthesized as above ・P-6: Epoxy resin (EPICION N-690, manufactured by DIC CORPORATION)

[Polymerizable compound] B-1: Shin-Nakamura Chemical Co., Ltd. product, polyethylene glycol #200 dimethacrylate (4G) B-2: Shin-Nakamura Chemical Co., Ltd. product , A-TMMT B-3: Hexamethoxymethylmelamine B-4: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.) B-5: CELLOXIDE 2021P (manufactured by Daicel Corporation) B-6 : Tetraethylene glycol dimethacrylate B-7: EX-321L (manufactured by Nagase Chemtex Corporation) B-8: Ethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) B -9: A compound of the following structure B-10: A compound of the following structure [Chemical formula 71]

〔polymerization initiator〕 · C-1: Irgacure OXE-01 (manufactured by BASF Corporation) C-2: Irgacure OXE-02 (manufactured by BASF Corporation) · C-3: Irgacure 784 (manufactured by BASF Corporation) ・C-4: CPI-210S (manufactured by San-Apro Ltd.) C-5: G-1820 manufactured by LAMBSON C-6: TrisP-PA (α,α,α'-tris(4-hydroxyphenyl)-1-ethyl- 4-isopropylbenzene) The compound obtained by quininating the hydroxyl diazide naphthoquinone C-7: 1-phenyl-2-[(benzoyloxy)imino]-1-propanone ・C-8: 2,2'-Azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) C-9: PERHEXA 25Z (manufactured by NOF CORPORATION.) C-10: PERCUMYL D (manufactured by NOF CORPORATION.)

〔Metal adhesion improver〕 ・D-1: KBM-403 (3-glycidoxypropyltrimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd.) D-2: γ-ureidopropyltriethylsilane D-3: N-[3-(triethoxysilyl)propyl]maleamide · D-4: N-(3-(triethoxysilyl)propyl)-phthalic acid ・D-5: KBM-502 (3-methacryloxypropylmethyldimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd.)

〔Migration inhibitor〕 · E-1: 5-aminotetrazole

〔polymerization inhibitor〕 F-1: 2MeHQ (methoxyhydroquinone) F-2: TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dicarbonyl) · F-3: 4MeHQ (4-methoxyphenol) F-4: PBQ (p-benzoquinone)

〔Surfactant〕 ・G-1: MEGAFACE F444 (manufactured by DIC CORPORATION) ・G-2: MEGAFACE F470 (manufactured by DIC CORPORATION)

〔Base Generator〕 H-1: 1-[4-(2-hydroxyethyl)-1-piperidinyl (Piperidinyl)]-3-(2-hydroxyphenyl)-1-propanone

[Additives] - I-1: a compound of the following structure - I-2: a compound of the following structure, Et represents an ethyl group.・I-3: N-phenyldiethanolamine ・I-4: Compound with the following structure ・I-5: TrisP-PA (α,α,α'-tris(4-hydroxyphenyl)-1-ethyl -4-isopropylbenzene) [Chemical Formula 72]

〔Solvent〕 J-1: GBL (γ-butyrolactone) J-2: DMSO (Dimethylsulfone) J-3: EL (ethyl lactate) J-4: NMP (N-methyl-2-pyrrolidone) J-5: CP (cyclopentanone)

[table 3] Composition Film thickness (μm) processing 1 processing 2 processing 3 Process 4 Process 5 Example 1 1st composition Composition 1 5 Heating 170℃/1h Coating of Composition 8 i-ray exposure Develop with 2.38% TMAH aqueous solution for 60s dry etching 2nd composition Composition 1 5 Heating 170℃/10m Develop with 2.38% TMAH aqueous solution for 180s - - - 2 1st composition Composition 2 5 i-ray exposure Develop with 2.38% TMAH aqueous solution for 60s Heating 120℃/180s - - 2nd composition Composition 2 5 170℃/10m Develop with 2.38% TMAH aqueous solution for 180s - - - 3 1st composition Composition 3 10 i-ray exposure Develop with PGMEA for 240s Heating 120℃/180s - - 2nd composition Composition 3 10 170℃/5m Develop with PGMEA for 300s Heating 200℃/2h - - 4 1st composition Composition 4 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 4 10 150℃/5m Develop with cyclopentanone for 120s Heating 200℃/2h - - 5 1st composition Composition 5 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 5 10 150℃/5m Develop with cyclopentanone for 120s Heating 200℃/2h - - 6 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 6 10 130℃/5m Develop with cyclopentanone for 120s Heating 200℃/2h - - 7 1st composition Composition 7 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 7 10 150℃/5m Develop with cyclopentanone for 120s Heating 200℃/2h - - 8 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 9 3 150℃/5m Develop with cyclopentanone for 160s Heating 200℃/2h - - 9 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 10 3 150℃/5m Develop with cyclopentanone for 160s Heating 200℃/2h - - 10 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 11 3 150℃/5m Develop with cyclopentanone for 160s Heating 200℃/2h - - 11 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 3 10 170℃/5m Develop with PGMEA for 300s Heating 200℃/2h - - 12 1st composition Composition 12 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 12 10 150℃/5m Develop with cyclopentanone for 120s Heating 200℃/2h - - 13 1st composition Composition 13 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 13 10 150℃/5m Develop with cyclopentanone for 120s Heating 200℃/2h - -

[Table 4] Composition Film thickness (μm) processing 1 processing 2 processing 3 Process 4 Process 5 Example 14 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 14 5 130℃/5m Develop with cyclopentanone for 40s Heating 200℃/2h - - 15 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 15 5 130℃/5m Develop with cyclopentanone for 40s Heating 200℃/2h - - 16 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 16 5 130℃/5m Develop with cyclopentanone for 40s Heating 200℃/2h - - 17 1st composition Composition 6 10 i-ray exposure Develop with cyclopentanone for 40s Heating 120℃/180s - - 2nd composition Composition 17 5 130℃/5m Develop with cyclopentanone for 40s Heating 200℃/2h - -

〔Evaluation〕 ＜Creation of composite pattern＞ In each example, the first composition described in the table was applied to a silicon wafer by spin coating, and dried at 100° C. for 5 minutes on a hot plate to form the silicon wafer described in the table. Thick coating film. Thereafter, each treatment described in the table was implemented (treatment 1 to treatment 5, wherein the column described with "-" indicates that no treatment was performed).

<Example 1> After the first composition was spin-coated, it was heated under the conditions described in the table (treatment 1) as treatment 1, and a coating film having a film thickness described in the table was formed. Thereafter, Composition 8 was applied on the obtained coating film as Process 2 to form a coating film of 5 μm. As Process 3, the concave pattern (removal) was exposed via a mask using an i-ray exposure machine. Development was performed for 60 seconds with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution as Process 4 . The pattern of the obtained composition 8 was dry-etched to a mask as process 5, and the pattern of the 1st composition was obtained. The second composition is further coated on the pattern of the first composition formed in the previous step. After the treatment 1 of the second composition was performed, the development of the treatment 2 was performed to obtain a composite pattern.

<Example 2> After the first composition was spin-coated, the concave pattern (removal) was exposed through a mask using an i-ray exposure machine as a process 1 . Development was carried out for 60 seconds with a 2.38 mass % TMAH aqueous solution as Process 2 . Post-heating was performed under the conditions described in the table as treatment 3 to obtain a pattern of the first composition. The second composition is further coated on the pattern of the first composition formed in the previous step. After the treatment 1 of the second composition was performed, the development of the treatment 2 was performed to obtain a composite pattern.

<Example 3> After the first composition was spin-coated, the concave pattern was exposed (removed) using an i-ray exposure machine through a mask as process 1. Development was performed for 60 seconds with PGMEA (propylene glycol monomethyl ether acetate) as process 2. Post-heating was performed as process 3 to obtain a pattern of the first composition. The second composition is further coated on the pattern of the first composition formed in the previous step. After the treatment 1 of the second composition was performed, the development of the treatment 2 was performed to obtain a composite pattern.

<Example 4-17> After the first composition was spin-coated, the concave pattern was exposed (removed) using an i-ray exposure machine through a mask as process 1. Development was performed with cyclopentanone for 60 seconds as process 2. Post-heating was performed as process 3 to obtain a pattern of the first composition. The second composition is further coated on the pattern of the first composition formed in the previous step. After the treatment 1 of the second composition, the development of the treatment 2 was performed, and the heating of the treatment 3 was performed, thereby obtaining a composite pattern. Among them, in the treatment 2 of the second composition of Example 11, the treatment described in the aforementioned Example 3 was carried out.

＜Determination of pattern shrinkage＞ After the pattern of the first composition was formed, the pattern width at the top of the pattern of the first composition was measured using a cross-sectional SEM (cross-sectional observation by a scanning electron microscope). Set its pattern width to D1. Let the pattern width of all the processed composite patterns of the second composition be D2, set the case where D2-D1 is 0.5 μm or more as “judgment A”, and set the case of 0.2 μm or more and less than 0.5 μm as “Judgment A”. Judgment B", and the case where it was less than 0.2 μm was set as "judgment C". The evaluation results are described in the column of "judgment of shrinkage" in the following table. It can be said that the larger D2-D1 is, the finer the pattern can be formed.

＜Judgement of reliability evaluation＞ Except having changed the silicon wafer into the base material which has the copper pattern of 10 micrometers LS (line and space), the composite pattern was provided on the copper pattern by the method similar to the said Examples 1-17. The substrate was placed in an oven at 175° C. for 500 hours. Thereafter, the base material was taken out from the oven, and the cross section was cut with an ion milling device, and the cross section was observed with a SEM (scanning electron microscope). The case where there is no peeling between the copper-resin film is set as "judgment A", and the case where the ratio of the peeled portion on the copper-resin film surface exceeds 0% and is less than 20% is set as "judgment B". When the ratio of the peeling part on the copper-resin film surface exceeded 20%, it was set as "judgment C". The evaluation results are described in the column of "presence or absence of peeling after HTS" in the following table. HTS stands for High Temperature Storage Test (high temperature storage test), and it can be said that the less peeling, the better the adhesion after the reliability test, that is, the less peeling will occur after a long period of time.

<Measurement of elongation at break> Except that the silicon wafer was changed to an 8-inch wafer having a copper oxide film, a composite pattern was provided on the copper oxide film by the same method as in the above-mentioned Examples 1 to 17. In the case of i-ray exposure, one capable of forming a pattern of 30×40 mm was used as a photomask. After finishing all the treatments described in the above table for the second composition, it was slowly cooled, and then immersed in 2N (2mol/L)-hydrochloric acid for 2 hours to peel off the film of the resin composition from the wafer , and after washing with water, a 30x4mm strip-shaped film of the composite pattern of Examples 1 to 17 was obtained. Using a tensile measuring device INSTRON 5965 (manufactured by Instron Corporation), stretching was performed at a room temperature of 23.0° C. at a tensile speed of 5 mm/min, and the elongation at break was measured. Regarding the measurement, 6 strips were measured per one sample, and the average value of the upper 3 points was calculated from the results. The value of elongation at breaking point was 40% or more as "judgment A", 39% to 10% as "judgment B", and 9% or less as "judgment C". The evaluation results are described in the column of "elongation at break" in the following table. It can be said that the larger the elongation at breaking point, the better the film strength.

[table 5] Shrinkage Judgment Presence or absence of stripping after HTS elongation at break Example 1 Judgment C Judgment C Judgment C Example 2 Judgment C Judgment C Judgment C Example 3 Judgment C Judgment C Judgment C Example 4 Judgment B Judgment A Judgment A Example 5 Judgment B Judgment A Judgment A Example 6 Judgment B Judgment A Judgment A Example 7 Judgment B Judgment A Judgment A Example 8 Judgment A Judgment A Judgment A Example 9 Judgment A Judgment A Judgment A Example 10 Judgment A Judgment A Judgment A Example 11 Judgment C Judgment B Judgment B Example 12 Judgment B Judgment A Judgment A Example 13 Judgment B Judgment A Judgment A Example 14 Judgment A Judgment A Judgment A Example 15 Judgment A Judgment A Judgment A Example 16 Judgment A Judgment A Judgment A Example 17 Judgment A Judgment A Judgment A

[Table 6] relative permittivity Composition 6 3.1 Composition 14 2.9 Composition 17 2.8

The relative permittivity described in the above table was prepared and measured under the above-mentioned condition 1 for individual films.

From the above results, it can be seen that a fine pattern can be formed according to the method for manufacturing a permanent film of the present invention.

1: Substrate 2: 1st pattern 4: Area between patterns 6: Film of the second resin composition 8: Area where the film of the second resin composition is removed 10: 2nd pattern 12: The area between the patterns of the composite pattern

Fig. 1 is a schematic diagram showing an example of a method for producing a permanent film of the present invention.

1: Substrate

2: 1st pattern

4: Area between patterns

6: Film of the second resin composition

8: Area where the film of the second resin composition is removed

10: 2nd pattern

12: The area between the patterns of the composite pattern

Claims (16)

A method of manufacturing a permanent film, comprising: Using the first resin composition, forming a film of the first resin composition on the substrate to obtain a substrate with a first pattern; A step of applying a second resin composition on the substrate having the first pattern to form a film of the second resin composition on the first pattern and in a region between the first patterns; and A step of removing a part of the film of the second resin composition to form a second pattern in contact with the first pattern, A region between patterns in the composite pattern formed of the first pattern and the second pattern is narrower than a region between patterns in the first pattern. The manufacturing method of the cured film as described in Claim 1, wherein The aforementioned first resin composition is a negative radiation-sensitive resin composition. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The step of obtaining the substrate having the first pattern is a step of developing by solvent development after selectively exposing the first resin composition film. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The step of forming the second pattern is a step of removing a part of the film of the second resin composition by solvent development. The method for manufacturing a permanent film according to claim 1 or claim 2, which further includes performing the first pattern after the step of forming the film of the second resin composition and before the step of forming the second pattern and the step of heating the film of the aforementioned second resin composition. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The aforementioned second resin composition contains a thermal polymerization initiator. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The aforementioned second resin composition contains a resin having a polymerizable group. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The aforementioned second resin composition contains a compound having a polymerizable group and a fennel skeleton. The manufacturing method of the 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. The manufacturing method of the 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. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The obtained permanent film comprises polyimide or polybenzoxazole. The manufacturing method of the permanent film according to claim 1 or claim 2, which further includes a heating step after the step of forming the second pattern. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The elongation at break of the aforementioned composite pattern is 40% or more. The manufacturing method of the permanent film as described in Claim 1 or Claim 2, wherein The first pattern includes at least one of a hole pattern and a groove pattern. A method for manufacturing a laminate, which includes the method for manufacturing a permanent film described in any one of claim 1 to claim 14. A method of manufacturing a semiconductor device, which includes the method of manufacturing a permanent film according to any one of claim 1 to claim 14.

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