KR20230047461A - A method for producing a cured product, a method for producing a laminate, and a method for manufacturing an electronic device - Google Patents

Abstract

A method for producing a cured product capable of obtaining a cured product having excellent elongation at break even when cured at low temperature, a method for producing a laminate including the method for producing the cured product, and a method for producing the cured product or a method for producing the laminate It is to provide a manufacturing method of an electronic device that does. A method for producing a cured product includes a film formation step of applying a specific photosensitive resin composition on a substrate to form a film, an exposure step, a developing step using a developing solution containing at least one compound selected from the group consisting of a base and a base generator, and , including a heating step, and the content of water with respect to the total mass of the developer is 50% by mass or less.

Description

A method for producing a cured product, a method for producing a laminate, and a method for manufacturing an electronic device

The present invention relates to a method for producing a cured product, a photosensitive resin composition, a method for producing a laminate, and a method for manufacturing an electronic device.

Since resins such as polyimide are excellent in heat resistance, insulating properties, etc., they are applied to various applications. The use is not particularly limited, but when a semiconductor device for mounting is taken as an example, a pattern made of these resins may be used as a material for an insulating film or sealing material, or as a protective film. In addition, patterns made of these resins are also used as base films and cover lays for flexible substrates.

For example, in the above-mentioned use, resin such as polyimide is used in the form of a photosensitive resin composition containing a polyimide precursor.

Such a photosensitive resin composition is applied to a base material by, for example, application, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product in which the polyimide precursor is imidized on the base material. can be formed in

Since the photosensitive resin composition can be applied by a known coating method or the like and can form a fine pattern or a complex pattern by development, it can be said that the cured film has a high degree of freedom in design and is excellent in adaptability in manufacturing. there is. In addition to the high performance of polyimide and the like, from the viewpoint of excellent adaptability in manufacturing, a method for producing a cured product using a photosensitive resin composition containing a polyimide precursor is expected to be gradually developed for industrial applications.

For example, in Patent Document 1, at least one selected from the group consisting of (a) basic compounds and (b) amides, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. A developing solution for a photosensitive polyimide precursor containing a species of organic solvent is described.

In Patent Document 2, (A) basic compound and/or basic aqueous solution, (B) alcohol compound, (C) N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethyl Group consisting of acetamide, dimethylsulfoxide, hexamethylenephosphoric triamide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-acetyl-ε-caprolactam, and tetramethylenesulfone At least one solvent selected from and (D) a mixed solvent of a ketone compound, (A) 2 to 15 parts by weight, (B) 25 to 60 parts by weight, (C) 25 to 60 parts by weight , (D) is 2 to 15 parts by weight, and a developer solution for a photosensitive polyimide precursor formulated so that the total amount is 100 parts by weight is described.

Patent Document 1: Japanese Unexamined Patent Publication No. 11-233949 Patent Document 2: Japanese Unexamined Patent Publication No. 3-194559

Conventionally, it has been performed to apply a photosensitive resin composition containing a polyimide precursor to a substrate to form a film, expose and develop the film, and then imidize the precursor by heating to produce a cured product. . By imidation, the mechanical properties (eg, elongation at break) of the membrane are improved, and the reliability of the module is improved.

In the production of the cured product, it is desired to provide a method for producing a cured product capable of obtaining a cured product having excellent elongation at break even when cured at a low temperature.

Specifically, for example, the cured product is used as an interlayer insulating film for a redistribution layer.

Here, the substrate on which the insulating film is used is increasing in size from an 8-inch wafer size to a 12-inch panel level and a larger area. Further, in order to provide wiring such as copper wiring, the number of layers to be laminated gradually increases from one layer to two, three, four, and five layers.

With the increase in the number of layers of polyimide and the increase in the number of layers of polyimide and the increase in the area of such a base during manufacturing, warpage of wafers and panels has become remarkable, and the above-mentioned heating is performed at a low temperature (eg, 240 ° C. or less, preferably 200 ° C.) below, more preferably at 180°C or below).

However, when the above-mentioned heating is performed at a low temperature, the imidation does not proceed sufficiently and the elongation at break of the film may decrease.

Until now, even when heating is performed at low temperature, it has been tried to introduce a base into the photosensitive resin composition for the purpose of sufficiently advancing imidation.

When a base is directly added to the photosensitive resin composition, imidation of the polyimide precursor proceeds even during storage of the photosensitive resin composition, and the viscosity of the composition may change remarkably.

When a photobase generator, which is a precursor of a base, is added, an acid and a radical that promote negative image formation are simultaneously generated in the exposure area during exposure, and a base that is an inhibitor of the acid and radical is simultaneously generated, resulting in a decrease in sensitivity. there was a case Moreover, it is difficult to add a base generator in large quantities to a composition on prescription, and the effect of promoting imidation at the time of heating was limited.

The present invention relates to a method for producing a cured product capable of obtaining a cured product having excellent elongation at break even when cured at a low temperature, a method for producing a laminate including the method for producing the cured product, and a method for producing the cured product or the laminate It is an object of the present invention to provide a manufacturing method of an electronic device including a manufacturing method.

Examples of representative embodiments of the present invention are shown below.

<1> A film formation step of applying a polyimide precursor having a repeating unit represented by the following formula (2) and a photosensitive resin composition containing a photopolymerization initiator onto a substrate to form a film;

An exposure step of selectively exposing the film to light;

A developing step of forming a pattern by developing the film after exposure with a developing solution containing at least one compound selected from the group consisting of a base and a base generator; and

A heating step of heating the pattern obtained by the development,

The method for producing a cured product, wherein the content of water with respect to the total mass of the developer is 50% by mass or less.

[Formula 1]

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

<2> The method for producing a cured product according to <1>, wherein the developing solution contains an organic base as the base.

<3> In the heating step, the polyimide precursor is imidized in the pattern by the action of at least one compound selected from the group consisting of the base and a base generated from the base generator by heating. The method for producing a cured product according to <1> or <2>, which is a step of accelerating.

<4> The method for producing a cured product according to any one of <1> to <3>, wherein the heating temperature in the heating step is 120 to 230°C.

<5> The method for producing a cured product according to any one of <1> to <4>, wherein the developing step is a step of supplying the developing solution to the film after exposure by showering or continuously supplying the developing solution.

<6> The method for producing a cured product according to any one of <1> to <5>, wherein the development in the developing step is negative development.

<7> The manufacturing method of the laminated body which repeats the manufacturing method of the hardened|cured material in any one of <1>-<6> multiple times.

<8> The manufacturing method of the laminated body as described in <7> which further includes the metal layer formation process of forming a metal layer on hardened|cured material between the manufacturing methods of the said hardened|cured material performed in multiple times.

<9> The manufacturing method of an electronic device including the manufacturing method of the hardened|cured material in any one of <1>-<6>, or the manufacturing method of a laminated body as described in <7> or <8>.

According to the present invention, even when cured at a low temperature, a method for producing a cured product capable of obtaining a cured product having excellent elongation at break, a method for producing a laminate including the method for producing the cured product, and a method for producing the cured product or the laminate A manufacturing method of an electronic device including a manufacturing method of is provided.

EMBODIMENT OF THE INVENTION Hereinafter, the main embodiment of this invention is described. However, the present invention is not limited to the specific embodiments.

In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively.

In this specification, the word "process" is meant to include not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.

In the notation of a group (atomic group) in this specification, the notation that does not describe substitution and unsubstitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" 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, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of light used for exposure include bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron beams, or radiation.

In the present specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acryl" refers to "acryl" and "methacryl". “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.

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

In this specification, the total solid content refers to the total mass of the components excluding the solvent from all components of the composition. Moreover, in this specification, 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, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values, unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220GPC (manufactured by Tosoh Co., Ltd.), and as a column, guard column HZ-L, TSKgel Super HZM- It can be obtained by using M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (above, manufactured by Tosoh Corporation) connected in series.

These molecular weights shall be measured using THF (tetrahydrofuran) as an eluent unless otherwise specified. However, 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, detection in the GPC measurement assumes that a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used unless otherwise specified.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", the reference layer among a plurality of layers of interest It is only necessary if there is another layer on the upper or lower side. That is, a third layer or element may be further interposed between the layer serving as the standard and the other layer, and the layer serving as the standard and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which layers are laminated with respect to the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", The opposite direction is referred to as "lower". Note that the setting of such a vertical direction is for convenience in this specification, and in an actual aspect, there may be cases where the “upper” direction in this specification is different from vertically upward.

In this specification, as long as there is no special description, a composition may also contain two or more types of compounds corresponding to the component as each component contained in a composition. 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, a combination of preferable aspects is a more preferable aspect.

(Method of producing cured product)

The method for producing a cured product of the present invention applies a photosensitive resin composition containing a polyimide precursor (hereinafter also referred to as "specific resin") having a repeating unit represented by formula (2) below, and a photopolymerization initiator onto a substrate. a film formation step of forming a film by applying a process, an exposure process of selectively exposing the film to light, and a developing process of forming a pattern by developing the exposed film with a developer containing at least one compound selected from the group consisting of a base and a base generator. , and a heating step of heating the pattern obtained by the development, wherein the content of water with respect to the total mass of the developing solution is 50% by mass or less.

[Formula 2]

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

According to the method for producing a cured product of the present invention, a cured product having excellent elongation at break can be obtained even when the cured product is cured at a low temperature.

Although the mechanism by which the said effect is obtained is unknown, it is guessed as follows.

In the method for producing a cured product of the present invention, as a developing solution, a developing solution containing at least one compound selected from the group consisting of bases and base generators is used.

It is thought that by using such a developing solution, at the time of development, at least one of the base and the base generator contained in the developing solution permeates the pattern obtained by development.

Due to the action of at least one of the base or base generator transferred from the developing solution to the pattern, the above-mentioned polyimide precursor is likely to imidize even at low temperatures, and it is estimated that significant lowering of the temperature can be realized during heating.

Here, in Patent Documents 1 and 2, a photosensitive resin composition containing a polyimide precursor having a repeating unit represented by the formula (2) and a photopolymerization initiator is used, and further selected from the group consisting of a base and a base generator. Forming a pattern by developing the film after exposure with a developing solution containing at least one compound is not described.

Hereinafter, the method for producing the cured product of the present invention will be described in detail.

<Film formation process>

The method for producing a cured product of the present invention includes a film forming step of forming a film by applying the photosensitive resin composition onto a substrate.

Details of the photosensitive resin composition (hereinafter, simply referred to as "resin composition") used in the present invention will be described later.

〔write〕

The type of base material can be appropriately determined depending on the application, but semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, Ni , metal substrates such as Cu, Cr, and Fe (for example, a substrate formed of metal and a substrate in which a metal layer is formed, for example, by plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates of plasma display panels (PDP), and the like, are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

In addition, layers such as an adhesion layer or an oxide layer by hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

In addition, the shape of the substrate is not particularly limited, and may be circular or rectangular.

As the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm.

Moreover, as a base material, for example, a plate shape, preferably a panel shape base material (substrate) is used.

In the case of forming a film by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured material) or the surface of a metal layer, the resin layer or metal layer serves as the base material.

As a means for applying the resin composition of the present invention onto a substrate, application is preferable.

As the means to be applied, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, ink jet law, etc. From the viewpoint of uniformity of film thickness, more preferably a spin coating method, a slit coating method, a spray coating method, or an inkjet method. From the viewpoint of uniformity of film thickness and productivity, the spin coating method and the slit coating method are preferred. do. A film having a desired thickness can be obtained by adjusting the solid content concentration of the resin composition and application conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferable, and for rectangular substrates, slit coating, spray coating, and inkjet methods are preferred. etc. are preferred. In the case of the spin coating method, it can be applied for about 10 seconds to 3 minutes at a rotational speed of 500 to 3,500 rpm, for example.

Moreover, a method of transferring onto a base material a coating film applied and formed on a temporary support body in advance by the above application method can also be applied.

Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP2006-023696 and paragraphs 0096 to 0108 of JP2006-047592 can be suitably used in the present invention.

Moreover, you may perform the process of removing an excess film|membrane in the edge part of a base material. Examples of such a process include edge bead rinse (EBR), back rinse, and the like.

Alternatively, a pre-wet process may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.

<Drying process>

The film may be subjected to a step of drying the formed film (layer) in order to remove the solvent after the film formation step (layer formation step) (drying step).

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step.

Moreover, it is preferable that the said drying process is performed after a film formation process and before an exposure process.

The film drying temperature in the drying step is preferably 50°C to 150°C, more preferably 70°C to 130°C, still more preferably 90°C to 110°C. Moreover, you may dry by reduced pressure. As drying time, 30 seconds - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 2 minutes - 7 minutes are more preferable.

<Exposure process>

The film is subjected to an exposure step of selectively exposing the film.

That is, the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed in the film formation step.

Exposing selectively means exposing a part of the film. Further, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed in the film.

The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but is preferably 50 to 10,000 mJ/cm ² , and 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, for example. more preferable

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

Regarding the exposure wavelength, in relation to the light source, (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), broad (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) , F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

In addition, the method of exposure is not particularly limited, and any method is sufficient as long as at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, and the like are exemplified.

<Post-exposure heating process>

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

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

The post-exposure heating step can be performed after the exposure step and before the developing step.

It is preferable that it is 50 degreeC - 140 degreeC, and, as for the heating temperature in the heating process after exposure, it is more preferable that it is 60 degreeC - 120 degreeC.

30 seconds - 300 minutes are preferable, and, as for the heating time in a heating process after exposure, 1 minute - 10 minutes are more preferable.

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

Moreover, you may change the temperature increase rate suitably in the middle of heating.

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

Moreover, it is also preferable to carry out in the atmosphere of low oxygen concentration by flowing an inert gas, such as nitrogen, helium, and argon, at the time of heating.

<Development process>

The method for producing a cured product of the present invention includes a developing step of forming a pattern by developing the film after exposure with a developing solution containing at least one compound selected from the group consisting of a base and a base generator.

By developing, one of an exposed part and a non-exposed part is removed, and a pattern is formed.

Here, a phenomenon in which the unexposed part is removed by the developing process is referred to as a negative-type phenomenon, and a phenomenon in which the exposed part is removed by the developing process is referred to as a positive-type phenomenon.

It is preferable that the development in the development process included in the manufacturing method of the hardened|cured material of this invention is negative development.

〔developer〕

The developing solution used in the method for producing a cured product of the present invention is a developing solution containing at least one compound selected from the group consisting of a base and a base generator, and the content of water with respect to the total mass of the developing solution is 50% by mass or less. .

When a developing solution containing at least one of a base and a base generator is used, as a result, a cured product having excellent elongation at break after heating is obtained. It is estimated that this is because the base in the developing solution immersed in the pattern promotes imidation in the heating step.

The water content is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The lower limit of the content of the water is not particularly limited, and may be 0% by mass.

-base-

It is preferable that a developing solution contains at least a base.

As the base contained in the developing solution, an organic base is preferable from the viewpoint of reliability (adhesion to the substrate when the cured product is further heated) when it remains in the film after curing.

As the base, a base having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, and the like are preferable. , tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, and secondary amines or tertiary amines are most preferred.

As the base, from the viewpoint of the mechanical properties (breaking elongation) of the cured product, one that is difficult to remain in the cured film (cured product obtained) is preferable, and from the viewpoint of promoting imidation, it is difficult to reduce the residual amount before heating by vaporization or the like. it is desirable

Therefore, the boiling point of the base is preferably 30°C to 350°C, more preferably 80°C to 270°C, and still more preferably 100°C to 230°C at normal pressure (101,325 Pa).

The boiling point of the base is preferably higher than the temperature obtained by subtracting 20°C from the boiling point of the organic solvent contained in the developing solution, and more preferably higher than the boiling point of the organic solvent contained in the developing solution.

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

Specific examples of the base contained in the developing solution include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldi Methylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecylamine) Sen), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1, 6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1, 2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole and the like.

When a base is included, the content of the base relative to the total mass of the developing solution is preferably 0.01 to 100% by mass, more preferably 0.05 to 20% by mass, still more preferably 0.1 to 10% by mass.

Moreover, when a base is not liquid at 10-30 degreeC, it is preferable that content of a base is 0.05-20 mass %, and it is more preferable that it is 0.1-10 mass %.

A base may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of bases together in a developing solution, it is preferable that the total content of them is within the above-mentioned range.

-base generator-

The developing solution may also contain a base generator.

Examples of the base generator include photobase generators and thermal base generators, and thermal base generators are preferred.

As the photobase generator or thermobase generator, for example, the photobase generator or thermobase generator described as a component contained in the photosensitive resin composition described later can be used without particular limitation.

When a base generator is included, the content of the base generator relative to the total mass of the developing solution is preferably 0.1 to 50% by mass, more preferably 0.2 to 20% by mass, and still more preferably 0.3 to 10% by mass. desirable.

A base generator may be used individually by 1 type, and may use 2 or more types together. When two or more types of base generators are used in combination in the developing solution, it is preferable that the total content thereof is within the above-mentioned range.

-solvent-

The developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 80% by mass or more, with respect to the total mass of the developing solution. The upper limit of the content of the organic solvent is not particularly limited, but is preferably 99.9% by mass or less, more preferably 99.8% by mass or less, still more preferably 99.5% by mass or less, and particularly preferably 99.0% by mass or less.

In the present invention, the developing solution preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula into ChemBioDraw.

The organic solvent is esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate , ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetic acid (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxyacetic acid) methyl, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg: 3-alkyloxymethylpropionate, 3-alkyloxyethylpropionate, etc.) (e.g., 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., 2-alkyl Methyl oxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g., 2-methoxy-2-methylmethylpropionate, ethyl oxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Col 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 aromatic hydrocarbons, such as toluene, xylene, anisole, etc., dimethyl sulfoxide as sulfoxides, and alcohols , N - Methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are mentioned suitably.

In addition, when the above-mentioned base (for example, organic base) is a liquid in the environment in which a developing solution is used, the above-mentioned base can be used as a solvent and a base.

In this invention, the organic solvent mentioned above can be used 1 type or in mixture of 2 or more types. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone and cyclohexanone are particularly preferred, and cyclopentanone, γ-butyrolactone and dimethyl sulfoxide are more preferred. Preferred, most preferred are those with cyclopentanone.

The developing solution may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[Supply Method of Developer]

The method of supplying the developer is not particularly limited as long as a desired pattern can be formed. A method of immersing a film-formed substrate in a developer, a puddle phenomenon in which a developer is supplied to a film formed on a substrate using a nozzle, or a developer is continuously applied. There is a way to supply. The type of nozzle is not particularly limited, and a straight nozzle and a shower nozzle are exemplified, and a spray nozzle and the like are exemplified as one type of shower nozzle.

From the viewpoints of permeability of the developer, removability of the non-image portion, and manufacturing efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a shower nozzle is preferable, and from the viewpoint of the permeability of the developer to the image portion, a shower The method of supplying with a nozzle is more preferable.

Alternatively, after continuously supplying the developing solution with a straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, a step of continuously supplying the developing solution with the straight nozzle again and then spinning the base material to remove the developing solution from the base material may be employed. , You may repeat this process multiple times.

Further, as a method for supplying the developing solution in the developing step, a step in which the developing solution is continuously supplied to the substrate, a step in which the developing solution is maintained on the substrate in a substantially stationary state, a step in which the developing solution is vibrated on the substrate with ultrasonic waves or the like, and a process in which they are combined. etc. can be employed.

Among these, it is preferable that the developing step is a step of supplying a developing solution to the film after exposure by showering or continuously supplying the developing solution.

As development time, 10 second - 10 minutes are preferable and 20 second - 5 minutes are more preferable. The temperature of the developing solution at the time of development is not particularly determined, but is preferably 10°C to 45°C, more preferably 18°C to 30°C.

In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with a rinsing solution. Moreover, you may employ|adopt the method of supplying a rinsing liquid while the developing solution which touches on a pattern is not completely dry.

As the rinse liquid, for example, a solvent different from the solvent contained in the developing solution (for example, an organic solvent different from the organic solvent contained in the developing solution) can be used.

Moreover, you may use the solvent contained in a developing solution as a rinse liquid.

The rinse liquid may further contain water in addition to the solvent.

Moreover, the rinse liquid may further contain at least one compound selected from the group consisting of bases and base generators contained in the above-mentioned developing solution.

The rinse time is not particularly limited, but can be, for example, 5 seconds to 5 minutes, preferably 10 seconds to 2 minutes.

<Heating process>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) is subjected to a heating step of heating the pattern obtained by the above development.

That is, the manufacturing method of the hardened|cured material of this invention includes the heating process of heating the pattern obtained by the image development process.

Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method or a film obtained by the film forming step without performing the developing step.

In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide.

Further, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds.

The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 160 to 250°C, and still more preferably 150 to 230°C.

The heating step is a step of accelerating imidation of the polyimide precursor in the pattern by the action of at least one compound selected from the group consisting of the base and a base generated from the base generator by heating. It is desirable to be

The heating in the heating step is preferably performed at a temperature rising 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 to 1 ° C./min or more, excessive volatilization of the acid or solvent can be prevented while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, residual stress of the cured product can be relaxed.

Further, in the case of an oven capable of rapid heating, heating is performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec. desirable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the time of starting the process of heating to the highest heating temperature. For example, when the resin composition of the present invention is applied on a substrate and then dried, the temperature of the film (layer) after this drying is, for example, 30 to higher than the boiling point of the solvent contained in the resin composition of the present invention. It is preferable to raise the temperature from a temperature as low as 200°C.

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

In particular, in the case of 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 120°C or higher, from the viewpoint of adhesion between the layers of the pattern. desirable.

The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, still more preferably 230°C or lower, and particularly preferably 200°C or lower.

Although the reason for this is not certain, it is considered that the ethynyl groups of the specific resin between the layers advance the crosslinking reaction by setting it at this temperature.

Heating may be performed stepwise. As an example, a process such as raising the temperature from 25 ° C to 120 ° C at 3 ° C / min, holding at 120 ° C for 60 minutes, raising the temperature from 120 ° C to 180 ° C at 2 ° C / min and holding at 180 ° C for 120 minutes You can do it. Moreover, it is also preferable to process while irradiating an ultraviolet-ray as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in a short time of about 10 second - about 2 hours, and 15 second - 30 minutes are more preferable. The pretreatment may be carried out in two or more stages, for example, the first stage pretreatment step may be performed in the range of 100 to 150 ° C., and then the second stage pretreatment step may be performed in the range of 150 to 200 ° C.

Moreover, you may cool after heating, and as a cooling rate in this case, it is preferable that it is 1-5 degrees C/min.

The heating step is preferably carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon or under reduced pressure to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

Although it does not specifically limit as a heating means in a heating process, For example, a hot plate, an infrared furnace, an electrothermal oven, a hot air oven, an infrared oven, etc. are mentioned.

<Exposure process after development>

The method for producing a cured product of the present invention may further include, in addition to the heating step, a post-development exposure step of exposing the pattern after the development step.

In the post-development exposure step, for example, a photobase generator that is a photosensitive compound described below is photosensitized, cyclization of the polyimide precursor proceeds, and a cured pattern is obtained.

In the post-development exposure process, at least a part of the pattern obtained in the development process may be exposed, but it is preferable that all of the patterns are exposed.

The exposure amount in the post-development exposure step 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 has sensitivity.

The post-development exposure process can be performed using, for example, the light source in the exposure process described above, and broadband light is preferably used.

<Metal layer formation process>

The pattern obtained by the developing step (preferably applied to the heating step) may be subjected to a metal layer forming step of forming a metal layer on the pattern.

That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern (preferably applied to a heating step) obtained by the developing step.

As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals are exemplified, and copper and Aluminum is more preferred, and copper is more preferred.

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

The thickness of the metal layer is preferably 0.01 μm to 50 μm, and more preferably 1 μm to 10 μm in the thickest part.

<Use>

Examples of the manufacturing method of the cured product of the present invention or applicable fields of the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, pattern formation of a sealing film, a substrate material (a base film or cover lay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting use as described above by etching may be used. Regarding these applications, for example, Science & Technology Co., Ltd. "Highly functional polyimide and application technology" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Basics and development of polyimide materials" November 2011 Monthly publication, Japanese Polyimide/Aromatic Polymer Research Society/edition "Latest Polyimide Basics and Applications" N.T.S., August 2010, etc. can be referenced.

In addition, the production method of the cured product of the present invention or the cured product of the present invention is used for producing a plate surface such as an offset plate surface or a screen plate surface, for use in etching of molded parts, in electronics, in particular, as a protective lacquer in microelectronics, and It can also be used for production of dielectric layers and the like.

(Laminate and manufacturing method of the laminate)

The laminate of the present invention refers to a structure having a plurality of layers comprising a cured product of the present invention.

The laminate of the present invention is a laminate comprising two or more layers of cured material, and may be a laminate of three or more layers.

At least one of the two or more layers of the cured material included in the laminate is a layer made of the cured material of the present invention, and from the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to the shrinkage, It is also preferable that all the layers made of the cured material included in the laminate are layers made of the cured material of the present invention.

That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to include repeating the manufacturing method of the laminated body of this invention multiple times.

It is preferable that the layered product of the present invention includes two or more layers of layers made of a cured product and includes a metal layer between any one of the layers made of the cured product. It is preferable that the said metal layer is formed by the said metal layer formation process.

That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation process of forming a metal layer on the layer which consists of hardened|cured material between the manufacturing method of hardened|cured material performed multiple times. Preferred aspects of the metal layer forming process are as described above.

As the above-mentioned laminate, a laminate containing at least a layered structure in which three layers, for example, a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order, is mentioned as a preferable one. .

It is preferable that both the layer composed of the first cured material and the layer composed of the second cured material are layers made of the cured material of the present invention. The resin composition of the present invention used for forming the layer composed of the first cured material and the resin composition of the present invention used for forming the layer composed of the second cured material may be compositions having the same composition or different in composition. It may be a composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Laminating process>

It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process.

The lamination step is, on the surface of the pattern (resin layer) or metal layer, (a) film formation step (layer formation step), (b) exposure step, (c) developing step, and (d) heating step in this order. It is a series of steps including performing with However, an aspect in which the film formation step of (a) and the heating step (d) are repeated may be used. Moreover, you may include (e) metal layer formation process after (d) heating process. It goes without saying that the above drying step or the like may be appropriately further included in the lamination step.

When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the exposure process, the heating process, or the metal layer forming process. As the surface activation treatment, plasma treatment is exemplified. Details of the surface activation treatment will be described later.

It is preferable to perform the said lamination process 2 to 20 times, and it is more preferable to perform it 2 to 9 times.

For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably composed of 2 or more layers and 20 or less layers, and more preferably 2 or more layers and 9 or less layers. .

Each of the above layers may be the same or different in composition, shape, film thickness, and the like.

In this invention, after providing a metal layer especially, the aspect which further forms the hardened|cured material (resin layer) of the said resin composition of this invention so that the said metal layer may be covered is preferable. Specifically, (a) film formation process, (b) exposure process, (c) development process, (d) heating process, (e) metal layer formation process, or (a) film formation process , (d) a heating step, and (e) an aspect of repeating the metal layer forming step in this order. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) of the present invention and the metal layer can be laminated alternately.

(Surface activation treatment process)

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 resin composition layer to a surface activation treatment.

The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after performing the surface activation treatment step on the resin composition layer after the above development step.

The surface activation treatment may be performed on at least a portion of the metal layer, at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region where the resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, adhesion to the resin composition layer (film) provided on the surface can be improved.

In addition, it is preferable to perform the surface activation treatment also on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to surface activation treatment, adhesion to the metal layer or resin layer provided on the surface of the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as in the case of negative development, it is difficult to receive damage by surface treatment and the adhesion is easy to improve.

As the surface activation treatment, specifically, plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixture gas, argon/oxygen mixture gas, etc.), corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ After etching treatment by /O ₂ , surface treatment by ultraviolet (UV) ozone method, and immersion in an aqueous hydrochloric acid solution to remove the oxide film, having at least one amino group and thiol group It is selected from an immersion treatment for an organic surface treatment agent containing a compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferred, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

(Method of manufacturing electronic device)

The present invention also discloses a method for manufacturing an electronic device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of an electronic device using the resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, the description of paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the description of FIG. 1 can be referred to. incorporated into the specification.

(Photosensitive Resin Composition)

The photosensitive resin composition is the photosensitive resin composition used in the manufacturing method of the cured product of the present invention, the manufacturing method of the layered product of the present invention, or the electronic device manufacturing method of the present invention.

The photosensitive resin composition of this invention contains the polyimide precursor which has a repeating unit represented by Formula (2), and a photoinitiator.

Hereinafter, the detail of each component contained in the photosensitive resin composition of this invention is demonstrated.

<specific resin>

The photosensitive resin composition contains the polyimide precursor (specific resin) which has a repeating unit represented by Formula (2).

Moreover, it is preferable that specific resin has a radical polymerizable group.

When the specific resin has a radical polymerizable group, the photosensitive resin composition preferably contains a radical photopolymerization initiator described later as a photopolymerization initiator, further includes a radical photopolymerization initiator described later, and further includes a radical crosslinking agent described later. It is more preferable, and it is still more preferable that a radical photopolymerization initiator described later is included, a radical crosslinking agent described later is included, and a sensitizer described later is included. A negative photosensitive layer is formed from such a photosensitive resin composition, for example.

Moreover, specific resin may have a polarity converter, such as an acid-decomposable group.

When specific resin has an acid-decomposable group, it is preferable that the photosensitive resin composition contains the photo-acid generator mentioned later. From such a photosensitive resin composition, a chemically amplified positive photosensitive layer or negative photosensitive layer is formed, for example.

[Polyimide precursor]

The polyimide precursor used in the present invention contains a repeating unit represented by the following formula (2).

[Formula 3]

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

A ¹ and A ² in Formula (2) each independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.

R ¹¹¹ in Formula (2) represents a divalent organic group. Examples of the divalent organic group include a straight-chain or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, and examples include a straight-chain or branched aliphatic group of 2 to 20 carbon atoms, a cyclic aliphatic group of 3 to 20 carbon atoms, and a group containing 3 carbon atoms. An aromatic group of ~20 or a group comprising a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, - It is a group consisting of SO ₂ - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. As diamine used for manufacture of a polyimide precursor, linear or branched aliphatic, cyclic aliphatic, or aromatic diamine, etc. are mentioned. As for diamine, only 1 type may be used and 2 or more types may be used.

Specifically, it is preferably a diamine containing a group consisting of a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, It is more preferable that it is a diamine containing a C6-C20 aromatic group. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. Examples of the group containing an aromatic group include the following.

[Formula 4]

In the formula, A represents a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S- , -SO ₂ -, -NHCO-, or a group selected from combinations thereof, preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O) More preferably, a group selected from -, -S-, or -SO ₂ -, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or More preferably -C(CH ₃ ) ₂ -.

In the formula, * represents a binding site with another structure.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexyl three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl Ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-di Aminodiphenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) )sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4 -aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy) ) Benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1 ,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetra Aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4 '-Diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5' -Tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3 ,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl ) Octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1 ,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1, 5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-di Methylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino -2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro Romethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) C) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4 ,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluoro and at least one type of diamine selected from tolidine and 4,4'-diaminoquaterphenyl.

Moreover, Paragraph 0030 of International Publication No. 2017/038598 - the diamine (DA-1) of 0031 - (DA-18) are also preferable.

Moreover, the diamine which has 2 or more alkylene glycol units of Paragraph 0032 of International Publication No. 2017/038598 - 0034 in a main chain is also used preferably.

R ¹¹¹ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or - NHCO- or a group consisting of 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 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

Further, from the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

formula (51)

[Formula 5]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and 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 group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. can

[Formula 6]

In Formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in Formula (2).

As the diamine giving the structure of formula (51) or (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2 2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. are mentioned. You may use these by 1 type or in combination of 2 or more types.

R ¹¹⁵ in Formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing 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 binding site with another structure.

[Formula 7]

In Formula (5), R ¹¹² is a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-; It is preferably a group selected from -SO ₂ -, -NHCO-, and combinations thereof, and is a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, More preferably, a group selected from -S- and -SO ₂ -, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S It is more preferably a divalent group selected from the group consisting of - and -SO ₂ -.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic dianhydride. The polyimide precursor may contain only one type or two or more types of tetracarboxylic dianhydride residues as a structure corresponding to R ¹¹⁵ .

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

[Formula 8]

In Formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in 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, and 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride. Water, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Intertetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4- dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

Moreover, tetracarboxylic dianhydride (DAA-1) of Paragraph 0038 of International Publication No. 2017/038598 - (DAA-5) are also mentioned as a preferable example.

R ¹¹³ and R ¹¹⁴ in Formula (2) each independently represent a monovalent organic group. As a monovalent organic group, what contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group is preferable. Moreover, it is preferable that at least one of ^R113 and ^R114 contains a polymeric 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. As the polymerizable group, it is a group capable of undergoing a crosslinking reaction by the action of heat, a radical, or the like, 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, a benzoxazolyl group, a block isocyanate group, and an amino group. 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, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (eg, vinylphenyl group, etc.), (meth)acrylamide group, (meth)acryloyloxy group, group represented by following formula (III), etc. are mentioned, and group represented by following formula (III) is preferable.

[Formula 9]

In Formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.

In formula (III), * represents a binding site with another structure.

In 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 polyalkyleneoxy group.

Examples of suitable R ²⁰¹ include an alkylene group such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and a 1,2-butanediyl group. , 1,3-butanediyl group, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy group, ethylene group, alkylene groups such as propylene group, -CH ₂ CH(OH)CH ₂ - , A cyclohexyl group and a polyalkyleneoxy group are more preferable, and an alkylene group such as an ethylene group or a propylene group or a polyalkyleneoxy group is more preferable.

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

In Formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity converter 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 carboxy group. Acetal group, ketal group, silyl group, silylether group, tertiary alkyl An ester group or the like is preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.

Specific examples of acid decomposable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-bu A toxycarbonylmethyl group, a trimethylsilyl ether group, etc. are mentioned. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

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

Moreover, for the purpose of improving adhesion to a substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, an aspect using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like is exemplified as the diamine.

It is preferable that the repeating unit represented by Formula (2) is a repeating unit represented by Formula (2-A). That is, it is preferable that at least 1 sort(s) of the polyimide precursor used by this invention is a precursor which has a repeating unit represented by Formula (2-A). When a polyimide precursor contains the repeating unit represented by Formula (2-A), it becomes possible to widen the width|variety of exposure latitude more.

Formula (2-A)

[Formula 10]

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

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in Formula (2), and the preferred ranges are also the same. do.

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, structural isomers of the repeating unit represented by Formula (2) may be included. In addition, it goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of the formula (2).

As one Embodiment of the polyimide precursor in this invention, the aspect whose content of the repeating unit represented by Formula (2) is 50 mol% or more of all repeating units is mentioned. As for the said total content, it is more preferable that it is 70 mol% or more, it is still more preferable that it is 90 mol% or more, and it is especially preferable that it is more than 90 mol%. The upper limit of the said total content is not specifically limited, All the repeating units in the polyimide precursor except for the terminal may be repeating units represented by Formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, still more preferably 8,000 to 20,000.

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and still more preferably 2.2 or more. Although the upper limit of the degree of dispersion of the molecular weight of the polyimide precursor is not particularly set, 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 by weight average molecular weight/number average molecular weight.

Moreover, when a resin composition contains multiple types of polyimide precursor as a specific resin, it is preferable that the weight average molecular weight of at least 1 type of polyimide precursor, number average molecular weight, and dispersion degree are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by calculating the plurality of types of polyimide precursors as one resin are respectively within the above ranges.

[Method for Producing Polyimide Precursors, etc.]

The polyimide precursor and the like are, for example, a method of reacting tetracarboxylic dianhydride and diamine at low temperature, obtaining polyamic acid by reacting tetracarboxylic dianhydride and diamine at low temperature, and esterification using a condensing agent or an alkylating agent method, tetracarboxylic dianhydride and alcohol to obtain a diester, then diamine and a reaction in the presence of a condensing agent, tetracarboxylic dianhydride and alcohol to obtain a diester, and then the remaining dicarboxylic acid to be reacted It can be obtained using a method such as a method of acid halogenating using a logenizing agent and reacting with diamine. Among the above production methods, a method in which a diester is obtained by using tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is acid-halogenated using a halogenating agent and reacted with diamine is more preferable.

Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1-carbonyldioxy. -Di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, anhydrous trifluoroacetic acid, etc. are mentioned.

Examples of the alkylating agent include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. can be heard

Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

In the manufacturing method of a polyimide precursor etc., it is preferable to use an organic solvent in the case of reaction. 1 type may be sufficient as an organic solvent, and 2 or more types may be sufficient as it.

Although the organic solvent can be appropriately determined depending on the raw material, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide , dimethylformamide, tetrahydrofuran, γ-butyrolactone and the like are exemplified.

In the manufacturing methods of a polyimide precursor etc., it is preferable to add a basic compound at the time of reaction. 1 type of basic compound may be sufficient as it, and 2 or more types may be sufficient as it.

The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl- 4-aminopyridine etc. are illustrated.

-end sealant-

In order to further improve the storage stability during production of the polyimide precursor or the like, it is necessary to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin end of the polyimide precursor or the like. When sealing the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal blocker include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. , It is more preferable to use phenols or monoamines. Moreover, especially from the viewpoint of reactivity and film stability, alcohols and phenols are preferable, and alcohols are more preferable. Preferable monoalcohol compounds include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and the like. secondary alcohols such as tertiary alcohol, isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. there is. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Moreover, as a compound of preferable monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 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-aminobenzene Sulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiocyanate Ophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

In addition, when sealing the amino group at the terminal of the resin, it is possible to seal with a compound having a functional group capable of reacting with the amino group. Preferred sealing agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides and the like, more preferably carboxylic acid anhydrides and carboxylic acid chlorides. Acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride etc. are mentioned as a preferable compound of carboxylic acid anhydride. Further, preferred compounds of the carboxylic acid chloride include acetyl chloride, acrylate chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-a damantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride and the like.

-solid precipitation-

In the case of manufacture of a polyimide precursor etc., you may include the process of depositing solid. Specifically, after the absorption by-product of the dehydration condensation agent coexisting in the reaction solution is separated by filtration as necessary, the obtained polymer component is introduced into a poor solvent such as water, lower aliphatic alcohol, or a mixture thereof, , A polyimide precursor etc. can be obtained by precipitating a polymer component, making it precipitate as a solid, and drying. In order to improve the degree of purification, operations such as re-dissolving the polyimide precursor, re-precipitation, and drying may be repeated. Further, 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 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and 50% by mass with respect to the total solid content of the resin composition. More than that is more preferable. Further, 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 or less with respect to the total solid content of the resin composition. It is more preferable that it is mass % or less, and it is still more preferable that it is 95 mass % or less.

The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When including 2 or more types, it is preferable that a total amount becomes the said range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resin.

Specifically, the resin composition of the present invention may contain a total of two or more types of specific resin and other resins described later, or may contain two or more types of specific resin, but preferably contains two or more types of specific resin. .

When the resin composition of the present invention contains two or more types of specific resin, for example, two or more types of polyimide precursors having different structures derived from dianhydride (R ¹¹⁵ in the above formula (2)) as polyimide precursors It is preferable to include.

<Other resins>

The resin composition of the present invention may also contain the specific resin described above and another resin different from the specific resin (hereinafter, simply referred to as “other resin”).

Examples of other resins include polyamideimide, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, and urethane resins. , butyral resin, styryl resin, polyether resin, polyester resin and the like.

For example, by further adding a (meth)acrylic resin, a resin composition excellent in applicability is obtained, and a pattern (cured product) excellent in solvent resistance is obtained.

For example, instead of the polymerizable compound described later or in addition to the polymerizable compound described later, the weight average molecular weight has a high polymerizable value of 50,000 or less (for example, the molar amount of the polymerizable group in 1g of the resin is 1 × 10 ⁻³ mol/g or more) (meth)acrylic resin can be added to the resin composition to improve the coating properties 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 should just exceed 0% by mass with respect to the total solid content of the resin composition, but it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. .

Further, the content of other resins in the resin composition of the present invention is preferably 30% by mass or more, more preferably 20% by mass or more, and even more preferably 10% by mass or more with respect to the total solid content of the resin composition. .

The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When including 2 or more types, it is preferable that a total amount becomes the said range.

[Photoinitiator]

The photosensitive resin composition contains a photoinitiator.

The photopolymerization initiator is preferably a radical photopolymerization initiator. The photo-radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators. For example, photoradical polymerization initiators having photosensitivity to light rays in the visible range from the ultraviolet range are preferred. Moreover, it may be an activator that generates an active radical by generating some kind of action with a photoexcited sensitizer.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L·mol ^-1 ·cm ^-1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). desirable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ultraviolet and visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

As an optical radical polymerization initiator, a known compound can be used arbitrarily. For example, acylphosphine compounds such as halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.) and acylphosphine oxides. , oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, hydroxyacetophenone, etc. α-hydroxy ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like. About these details, Paragraph 0165 of Unexamined-Japanese-Patent No. 2016-027357 - 0182 and Paragraph 0138 of International Publication No. 2015/199219 - description of 0151 can be considered into consideration, and this content is integrated in this specification. In addition, Paragraphs 0065 to 0111 of Unexamined-Japanese-Patent No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, MATERIAL STAGE 37-60p, vol. 19, no. 3, a peroxide-based photopolymerization initiator described in 2019, a photopolymerization initiator described in International Publication No. 2018/221177, a photopolymerization initiator described in International Publication No. 2018/110179, a photopolymerization initiator described in Japanese Unexamined Patent Publication No. 2019-043864, The photoinitiator described in Unexamined-Japanese-Patent No. 2019-044030, and the peroxide-type initiator described in Unexamined-Japanese-Patent No. 2019-167313 are mentioned, These content is also integrated in this specification.

As a ketone compound, the compound of Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, This content is integrated in this specification. As a commercial item, Kayacure-DETX-S (Nippon Kayaku Co., Ltd. product) is also used suitably.

In one embodiment of the present invention, as the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Unexamined Patent Publication No. 10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can be used, the contents of which are described herein. is used for

As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade name: all manufactured by BASF) can be used.

As the α-aminoketone initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: both manufactured by BASF) can be used.

As an aminoacetophenone system initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 in which absorption maximum wavelength was matched with wavelength light sources, such as 365 nm or 405 nm, can also be used, The content is integrated in this specification.

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

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

As an optical radical polymerization initiator, an oxime compound is mentioned more preferably. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As a specific example of an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2001-233842, the compound described in Unexamined-Japanese-Patent No. 2000-080068, the compound described in Unexamined-Japanese-Patent No. 2006-342166, J. C. S. Perkin II (1979, pp 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Laid-Open Patent Publication A compound described in Japanese Patent Publication No. 2000-066385, a compound described in Japanese Patent Publication No. 2004-534797, a compound described in Japanese Patent Laid-Open No. 2017-019766, a compound described in Japanese Patent Publication No. 6065596, International Publication No. 2015/152153 A compound described in, a compound described in International Publication No. 2017/051680, a compound described in Japanese Unexamined Patent Publication No. 2017-198865, a compound described in Paragraph Nos. 0025 to 0038 of International Publication No. 2017/164127, International Publication No. 2013 /167515, etc. are mentioned, The content of this is integrated in this specification.

Preferable examples of the oxime compound include compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy ) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of this invention, it is especially preferable to use an oxime compound (oxime type radical photopolymerization initiator) as an optical radical polymerization initiator. An oxime-based photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in its molecule.

[Formula 11]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., optical The radical polymerization initiator 2) is also suitably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), Adeka Akles NCI-730, NCI-831 and Deca Arcs NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used.

[Formula 12]

As the radical photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 and the compound of Unexamined-Japanese-Patent No. 06636081 are mentioned, The content is integrated in this specification.

As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring among carbazole rings has become a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned, This content is integrated in this specification.

Moreover, it is also possible to use the oxime compound which has a fluorine atom. As a specific example of such an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24, 36-40 described in Paragraph 0345 of Unexamined-Japanese-Patent No. 2014-500852, and Unexamined-Japanese-Patent No. 2013- and the compound (C-3) described in Paragraph 0101 of No. 164471, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound which has a nitro group as a dimer. As specific examples of the oxime compound having a nitro group, the compounds described in Paragraph Nos. 0031 to 0047 of Unexamined-Japanese-Patent No. 2013-114249, Paragraph Nos. 0008 to 0012, and 0070 to 0079 of Unexamined-Japanese-Patent No. 2014-137466, Japanese Patent Publication Paragraph No. 0007 of No. 4223071 - the compound described in 0025 are mentioned, The content of this is integrated in this specification. Moreover, as an oxime compound which has a nitro group, Adeka Akles NCI-831 (made by ADEKA Corporation) is also mentioned.

As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. As a specific example, OE-01 described in international publication 2015/036910 - OE-75 is mentioned.

As the radical photopolymerization initiator, an oxime compound having a substituent having a hydroxyl group bonded to the carbazole skeleton can also be used. As such a photoinitiator, the compound of international publication 2019/088055, etc. are mentioned, This content is integrated in this specification.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. Examples of the electron withdrawing group possessed by 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, and a cyano group, and an acyl group and A nitro group is preferable, and an acyl group is more preferable, and a benzoyl group is more preferable because it is easy to form a film having excellent light resistance. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and an alkoxy group, an alkylsulfanyl group or an amino group. it is more preferable

The oxime compound OX is preferably at least one selected from compounds represented by formula (OX1) and compounds represented by formula (OX2), and more preferably is a compound represented by formula (OX2).

[Formula 13]

In the formula, R ^X1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, represents an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;

R ^X2 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , Representing an acyloxy group or an amino group,

R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;

However, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

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

As a specific example of oxime compound OX, Paragraph No. 0083 of Japanese Patent Publication 4600600 - the compound of 0105 are mentioned, This content is integrated in this specification.

As the most preferable oxime compound, the oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned, The content of which is incorporated herein by reference.

Radical photopolymerization initiators are, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metal Rosene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxa Compounds selected from the group consisting of diazole compounds and 3-aryl-substituted coumarin compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds. , A benzophenone compound, an acetophenone compound, at least one selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds A compound of the species is more preferable, and it is even more preferable to use a metallocene compound or an oxime compound.

In addition, the radical photopolymerization initiator is N,N'-tetraalkyl-4,4'-diamino, such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone). Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholyl Aromatic ketones such as no-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyldi Benzyl derivatives, such as methyl ketal, etc. can also be used. Moreover, the compound represented by following formula (I) can also be used.

[Formula 14]

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

[Formula 15]

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

Moreover, as an optical radical polymerization initiator, Paragraph 0048 of International Publication No. 2015/125469 - the compound of 0055 can also be used, and this content is integrated in this specification.

As the radical photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. Since two or more radicals generate|occur|produce from one molecule of radical photopolymerization initiator by using such a radical photopolymerization initiator, favorable sensitivity is obtained. In addition, in the case of using a compound with an asymmetric structure, crystallinity is reduced, solubility in solvents and the like is improved, and it is difficult to precipitate over time, so that the stability over time of the resin composition can be improved. As a specific example of a bifunctional or trifunctional or more than trifunctional radical photopolymerization initiator, paragraphs of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, Japanese Patent Publication No. 2016-532675 Dimers of oxime compounds described in No. 0407 to 0412, Paragraph Nos. 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in Paragraph No. 0007 of Japanese Patent Publication No. 2017-523465, Paragraph Nos. 0020 to 0033 of Japanese Unexamined Patent Publication No. 2017-167399 , the photopolymerization initiator (A) described in Paragraph Nos. 0017 to 0026 of Japanese Unexamined Patent Publication No. 2017-151342, and the oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, etc., this content is incorporated herein.

Its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably It is 1.0-10 mass %. The 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 the total amount is the said range.

In addition, since a photoinitiator also functions as a thermal polymerization initiator in some cases, crosslinking by the photopolymerization initiator can be further promoted by heating in an oven, a hot plate or the like in some cases.

[sensitizer]

The resin composition may contain a sensitizer. A sensitizer absorbs specific actinic radiation and becomes an electronic excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, an optical radical polymerization initiator, and the like, and actions such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and photoradical polymerization initiator are decomposed by chemical change to generate radicals, acids or bases.

As usable sensitizers, benzophenone-based, Michler's ketone-based, coumarin-based, pyrazolazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyraline Compounds such as zolotriazolazo-based, pyridonazo-based, cyanine-based, phenothiazine-based, pyrrolopyrazolazomethane-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds can be used.

Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis( 4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4 '-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2 -(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1 ,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-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), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morphopoly Nobenzophenone, dimethylaminobenzoate isoamyl, diethylaminobenzoate isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p- Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide and the like.

Moreover, you may use another sensitizing dye.

About the detail of a sensitizing dye, Paragraph 0161 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0163 can be considered into consideration, and this content is integrated 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 with respect to the total solid content of the resin composition. It is more preferable to be 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, on pages 683-684 of the Polymer Dictionary, 3rd edition (ed., 2005). 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, used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compound and the like having a thiocarbonylthio group are used. These can generate radicals by donating hydrogen to radicals with low activity to generate radicals, or by deprotonating after being oxidized. In particular, a thiol compound can be preferably used.

Moreover, Paragraph 0152 of International Publication No. 2015/199219 - the compound of 0153 can also be used for a chain transfer agent, and this content is integrated 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, more preferably 0.1 to 10 parts by mass, and 0.5 parts by mass to 100 parts by mass of the total solid content of the resin composition of the present invention. -5 parts by mass is more preferred. 1 type of chain transfer agent may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of chain transfer agents, it is preferable that the sum total is the said range.

<Solvent>

It is preferable that the resin composition of this invention contains a solvent.

A well-known solvent can be used arbitrarily as a solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxy methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., 3-alkyloxymethylpropionate, 3-alkyloxy Ethyl propionate and the like (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (eg For example, 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy-2-methylpropionate) methyl, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, Ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are mentioned as suitable ones.

As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Lycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene 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, 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 mentioned as suitable ones.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like. can

As the cyclic hydrocarbons, suitable examples thereof include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.

As sulfoxides, for example, dimethyl sulfoxide is mentioned as a suitable one.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Formamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetyl Morpholine etc. are mentioned as a suitable thing.

As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. are mentioned as suitable ones.

As alcohols, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2- Propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Colmonomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono Phenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol, etc. are mentioned.

As for the solvent, a form in which two or more types are mixed is also preferable from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptane one, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One solvent selected from propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

The content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, from the viewpoint of applicability. It is more preferable to set it as an amount of - 70% by mass, and it is more preferable to set it as an amount of 20 - 70% by mass. What is necessary is just to adjust solvent content according to the desired thickness of a coating film, and a coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types of solvents. When containing 2 or more types of solvents, it is preferable that the sum total is the said range.

<Thermal acid generator>

The photosensitive resin composition may also contain a thermal acid generator.

The thermal acid generator generates an acid by heating and causes a crosslinking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound. has a stimulating effect.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, acid is not generated during drying (prebaking: about 70 to 140° C.) after coating the composition on a substrate, and at the time of final heating (curing: about 100 to 400° C.) after patterning by subsequent exposure and development. Selecting an acid-generating agent as the thermal acid generator is preferable because the decrease in sensitivity during development can be suppressed.

The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak having the lowest temperature when the thermal acid generator is heated in a pressure resistant capsule at 5°C/min to 500°C.

As a device used when measuring the thermal decomposition start temperature, Q2000 (manufactured by TA Instruments) and the like are exemplified.

The acid generated from the thermal acid generator is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. Haloalkylsulfonic acids, such as phonic acid or trifluoromethanesulfonic acid, etc. are preferable. As an example of such a thermal acid generator, the thing of Unexamined-Japanese-Patent No. 2013-072935 Paragraph 0055 is mentioned.

Among them, it is more preferable to generate an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms from the viewpoint of less residual in the cured product (cured film) and less difficulty in reducing the physical properties of the cured product (cured film). and methanesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, methanesulfonic acid benzyl (4-hydroxyphenyl) Methylsulfonium, methanesulfonate benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, trifluoro Romethenesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, trifluoromethanesulfonic acid benzyl (4 -Hydroxyphenyl)methylsulfonium, trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl (( 2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-iridene)-2-(o-tolyl)propanenitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane is preferable as the thermal acid generator.

Moreover, the compound of Paragraph 0059 of Unexamined-Japanese-Patent No. 2013-167742 is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, with respect to 100 parts by mass of the resin. Since the crosslinking reaction is accelerated by containing 0.01 part by mass or more, the mechanical properties and solvent resistance of the cured product (cured film) can be further improved. Moreover, from a viewpoint of the electric insulating property of hardened|cured material (cured film), 20 mass parts or less is preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are still more preferable.

<Base generator>

The resin composition of the present invention may also contain a base generator. Here, a base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.

In particular, when the resin composition contains a precursor of a cyclization resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be accelerated by, for example, heating, and the mechanical properties and chemical resistance of the cured product are improved, for example, for a redistribution layer included in a semiconductor package. The performance as an 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 according to the present invention is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, and nitrobenzylcarbamate compounds. , sulfonamide compound, imidazole derivative compound, amineimide compound, pyridine derivative compound, α-aminoacetophenone derivative compound, quaternary ammonium salt derivative compound, pyridinium salt, α-lactone ring derivative compound, amineimide compound, phthal Imide derivative compounds, acyloxyimino compounds and the like can be used.

As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned.

[Formula 16]

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. However, there is no case where Rb ¹ and Rb ² simultaneously become a hydrogen atom. In addition, none of Rb ¹ , Rb ² and Rb ³ have a carboxyl group. In addition, in this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited thereto.

In formulas (B1) and (B2), as for Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of these includes a cyclic structure, and it is more preferable that at least two of these include a cyclic structure. As the cyclic structure, either a monocycle or a condensed ring may be used, and a monocycle or a condensed ring in which two monocycles are condensed is preferable. A 5-membered ring or a 6-membered ring is preferable, and, as for a monocyclic ring, a 6-membered ring is preferable. As for a monocyclic ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, , 2 to 18 are more preferred, 3 to 12 are more preferred), an aryl group (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred), or an arylalkyl group ( It is preferably 7 to 25 carbon atoms, more preferably 7 to 19, more preferably 7 to 12). These groups may have a substituent within the range of exhibiting the effect of the present invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly preferably a straight-chain, branched, or cyclic alkyl group which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12). , It is more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and still more preferably 3 to 12) which may have a substituent, and a cyclohexyl group that may have a substituent is more preferable do.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and still more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, 6-10 are more preferable), an alkenyl group (C2-24 are preferable, 2-12 are more preferable, 2-6 are more preferable), an arylalkyl group (C7-23 are preferable, 7-12 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), an arylalkenyl group (C 8 to 24 is preferable, 8 to 20 are more preferable, and 8 to 16 are more preferable), an alkoxyl group (C 1 to C 16 is preferable) 24 is preferable, 2 to 18 are more preferable, 3 to 12 are more preferable), aryloxy group (C6 to 22 are preferable, 6 to 18 are more preferable, 6 to 12 are still more preferable) , or an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Especially, a cycloalkyl group (C3-C24 is preferable, 3-18 are more preferable, and 3-12 are still more preferable), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent within the range showing the effect of the present invention.

It is preferable that the compound represented by Formula (B1) is a compound represented by the following formula (B1-1) or the following formula (B1-2).

[Formula 17]

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in the formula (B1), respectively.

Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and 3 -12 is more preferable), aryl group (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are more preferable), and may have a substituent within the range showing the effect of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ are each independently a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms) and, more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group ( 7-23 carbon atoms are preferable, 7-19 are more preferable, and 7-11 are still more preferable), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3-8 are more preferable), aryl group (C6-22 are preferable, 6-18 are more preferable, 6-12 are more preferable), arylalkyl group (C7-23 are preferable, 7-18 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), and an aryl group is preferable.

As for the compound represented by formula (B1-1), the compound represented by formula (B1-1a) is also preferable.

[Formula 18]

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 a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms and 2 to 6 carbon atoms) More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10), an arylalkyl group (7 to 23 carbon atoms) preferably, 7 to 19 are more preferable, and 7 to 11 are still more preferable), and a hydrogen atom or a methyl group is preferable.

Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 3 to 8), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and 3 -8 is more preferable), aryl group (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are more preferable), and among them, an aryl group is preferable.

[Formula 19]

In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a link chain connecting adjacent oxygen atoms and carbon atoms, and a hydrocarbon group having 3 or more atoms on the path of the link chain. indicate Further, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, "linked chain" refers to linking these linking objects in the shortest (minimum number of atoms) among atomic chains on a path connecting between two atoms or groups of atoms to be linked. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, the linked chain is composed of 4 carbon atoms, and the number of atoms on the path of the linked chain ( That is, the number of atoms constituting the linked chain, hereinafter also referred to as “linked chain length” or “linked chain length”) is 4.

[Formula 20]

It is preferable that the number of carbon atoms in L in the formula (B3) (including carbon atoms other than carbon atoms in the link chain) is 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. As for a lower limit, it is more preferable that it is 4 or more. From the viewpoint of rapidly advancing the intramolecular cyclization reaction, the upper limit of the link 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. In particular, the length of the linked chain of L is preferably 4 or 5, and most preferably 4. As a specific preferable compound of a base generator, the compound of Paragraph No. 0102 - 0168 of International Publication No. 2020/066416, and the compound of Paragraph No. 0143 - 0177 of International Publication No. 2018/038002 are also mentioned, for example. .

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

[Formula 21]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, RC1 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. It is preferable that it is 1 or more, and, as for the length of the linked chain of a linking group, it is more preferable that it is 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and still more preferably 5 or less. Linked chain length is the number of atoms present in the atomic arrangement that forms the shortest path between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group. (C1-24 is preferable, 1-12 are more preferable, and 1-10 are more preferable), and specifically, an aliphatic hydrocarbon group (C1-24 is preferable, 1-12 is more preferable, more preferably 1 to 10) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and aliphatic carbonization Hydrogen groups are preferred. As R ^N1 and R ^N2 , it is preferable to use an aliphatic hydrocarbon group 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 or in the substituent. In particular, an aspect in which an aliphatic hydrocarbon group has an oxygen atom in a hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a straight-chain or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The straight-chain or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, and still more preferably 3 to 12. The straight chain or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, Isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, etc. are mentioned.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The group relating to the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, still more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.

The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 4. The alkyl group having an oxygen atom in its chain may be chain or cyclic, or may be straight or branched.

Among them, from the viewpoint of increasing the boiling point of the decomposition product base described later, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in formulations that place importance on adhesion when stacking with a layer of metal (for example, copper), a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

R ^N1 and R ^N2 may be connected to each other to form a cyclic structure. In forming a cyclic structure, you may have an oxygen atom etc. in a chain|strand. Further, the cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic or condensed ring, but a monocyclic structure is preferable. As the cyclic structure formed, a 5- or 6-membered ring containing a nitrogen atom in formula (N1) is preferable, and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, and an imidazolidine ring. , A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. are mentioned, A pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring are mentioned preferably.

R ^C1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.

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 preferably used.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Examples of the chain-like alkyl group having an oxygen atom in the chain include, specifically, an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

The divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or an oxygen atom in the chain A group related to a combination of a divalent aliphatic hydrocarbon group that may have a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.

The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, still more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, still more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and more preferably 7 to 10 desirable.

As the linking group L, specifically, a straight chain 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, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenyl A rene group, a cyclic alkenylene group, an arylene group, and an arylene alkylene group are preferable.

The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

The group relating to the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, still more preferably 4 to 6.

The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be straight or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3.

The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 3. The number of C=C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3.

The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2.

The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10.

The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11.

Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1 ,3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene A group (particularly a 1,2-phenylenemethylene group) and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

Examples of the base generator include the following examples, but the present invention is not construed as being limited thereto.

[Formula 22]

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

As a specific preferable compound of an ionic base generator, Paragraph No. 0148 of International Publication No. 2018/038002 - the compound of 0163 are also mentioned, for example.

Although the following compounds are mentioned as a specific example of an ammonium salt, this invention is not limited to these.

[Formula 23]

Although the following compounds are mentioned as a specific example of an iminium salt, this invention is not limited to these.

[Formula 24]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, or may be 4 parts by mass or less.

1 type or 2 or more types can be used for a base generator. When using 2 or more types, it is preferable that the total amount is the said range.

<Polymerizable compound>

It is preferable that the resin composition of this invention contains a polymeric compound.

As a polymeric compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical Crosslinking Agent]

It is preferable that the resin composition of this invention contains a radical crosslinking agent.

A 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 groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.

Among these, as a group containing the said ethylenically unsaturated bond, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and a (meth)acryloyl group is more preferable from a reactive viewpoint.

It is preferable that it is a compound which has one or more ethylenically unsaturated bonds, but, as for a radical crosslinking agent, it is more preferable that it is a compound which has two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

As the compound having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferable, compounds having 2 to 10 ethylenically unsaturated bonds are more preferable, and compounds having 2 to 6 this is more preferable

Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. .

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. As for the lower limit of the molecular weight of a radical crosslinking agent, 100 or more are preferable.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, preferably unsaturated These are esters of carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or a monofunctional or polyfunctional carboxylic acid Dehydration condensation reactants and the like are also suitably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, furthermore, a halo xeno group, a tosyloxy group, etc. Also suitable are substitution reactants of unsaturated carboxylic acid esters or amides having a leaving substituent with monofunctional or polyfunctional alcohols, amines, or thiols. In addition, as another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether in place of the above unsaturated carboxylic acid. As a specific example, Paragraph 0113 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0122 can be considered into consideration, and these content is integrated in this specification.

Moreover, the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanedioldi(meth)acrylate, trimethylolpropane tri(acryloyl Compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as oxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin or trimethylolethane, and then (meth)acrylated compounds, Japan Urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication Polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, epoxy acrylic which is a reaction product of epoxy resin and (meth)acrylic acid Polyfunctional acrylates and methacrylates, such as lates, and mixtures thereof are exemplified. Moreover, Paragraph 0254 of Unexamined-Japanese-Patent No. 2008-292970 - the compound of 0257 are also suitable. Moreover, the polyfunctional (meth)acrylate obtained by making the compound which has a cyclic ether group, such as glycidyl (meth)acrylate, and an ethylenically unsaturated bond react with polyfunctional carboxylic acid, etc. are mentioned.

In addition, as preferred radical crosslinking agents other than those described above, those described in Japanese Unexamined Patent Publication No. 2010-160418, Japanese Unexamined Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc., have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resin.

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. Hei 01-040337, and Japanese Patent Publication Hei 01-040336, and Japanese Unexamined Patent Publication Hei 02-025493 and the vinylphosphonic acid-based compounds described in No. Moreover, the compound containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-022048 can also be used. Also, Journal of the Japan Adhesion Association vol. 20, no. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300 to 308 (1984) can also be used.

In addition to the above, the compound of Paragraph 0048 of Unexamined-Japanese-Patent No. 2015-034964 - 0051, and the compound of Paragraph 0087 of International Publication No. 2015/199219 - 0131 can also be used preferably, These content is integrated in this specification.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Unexamined Patent Publication No. 10-062986, (meth)acrylated A compound can also be used as a radical crosslinking agent.

In addition, Paragraph 0104 of Unexamined-Japanese-Patent No. 2015-187211 - the compound of 0131 can also be used as a radical crosslinking agent, These content is integrated in this specification.

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

As a commercially available product of the radical crosslinking agent, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, 231, 239, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane Oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo), DPHA- 40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Nichiyu ( Note) and the like.

Examples of the radical crosslinking agent include those described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese Patent Publication No. Hei 02-016765. Retane acrylates, ethylene oxide systems described in Japanese Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, Japanese Publication No. 62-039418 Urethane compounds having a skeleton are also suitable. In addition, as a radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. Hei 01-105238 can be used. can also be used

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group do. Particularly preferably, in a radical crosslinking agent obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. am. As a commercial item, M-510, M-520 etc. are mentioned, for example as a Toagosei Co., Ltd. product polybasic acid modified acrylic oligomer.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. When the acid value of the radical crosslinking agent is in the above range, the handleability in production is excellent, and furthermore, the developability is excellent. Moreover, polymerizability is good. The said acid value is measured based on description of JISK0070:1992.

For the resin composition, it is preferable to use a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability.

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 , neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate rate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified die Acrylates, isocyanuric acid-modified dimethacrylates, and other bifunctional acrylates having a urethane bond and bifunctional methacrylates having a urethane bond can be used. These can mix and use 2 or more types as needed.

In addition, for example, PEG200 diacrylate is polyethylene glycol diacrylate, and means that the formula of a polyethylene glycol chain is about 200.

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 curvature suppression by controlling the modulus of elasticity of the pattern (cured product). As a monofunctional radical crosslinking agent, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylic acid derivatives such as mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl Ether and the like are preferably used. 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 a diallyl phthalate and triallyl trimellitate, are mentioned as a bifunctional or more than bifunctional radical crosslinking agent.

When containing a radical crosslinking agent, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solids of the resin composition of this invention. As for a lower limit, 5 mass % or more is more preferable. As for an upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less.

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

[Other crosslinking agents]

It is also preferable that the resin composition of this invention contains another crosslinking agent different from the radical crosslinking agent mentioned above.

In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and a covalent bond between the above-mentioned photoacid generator or photobase generator and other compounds in the composition or a reaction product thereof by photosensitization of the photoacid generator. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction to form a group in the molecule that promotes the reaction of forming a covalent bond with other compounds or reaction products thereof in the composition by the action of an acid or base. A compound having a plurality of them is preferred.

The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

As another crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is a nitrogen atom A compound having a structure directly bonded to is more preferred.

As another crosslinking agent, for example, formaldehyde or formaldehyde and alcohol are reacted with an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methyl and compounds having a structure substituted with an all group or an alkoxymethyl group. The manufacturing method of these compounds is not specifically limited, Any compound having the same structure as the compound manufactured by the said method is sufficient. Moreover, the oligomer formed by self condensation of the methylol groups of these compounds may be sufficient.

As the amino group-containing compound, a crosslinking agent using melamine is a melamine crosslinking agent, glycoluril, a crosslinking agent using urea or an alkylene urea is a urea crosslinking agent, a crosslinking agent using alkylene urea is an alkylene urea crosslinking agent, benzoguanamine A crosslinking agent using is called a benzoguanamine-based crosslinking agent.

Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and from the group consisting of a glycoluril-based crosslinking agent and a melamine-based crosslinking agent described later. It is more preferable to include at least one selected compound.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below, or on a triazine It can be mentioned as a structural example.

The alkoxymethyl group or acyloxymethyl group of the compound has preferably 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.

The total number of alkoxymethyl groups and acyloxymethyl groups of the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the compound is preferably 1500 or less, preferably 180 to 1200.

[Formula 25]

R ₁₀₀ represents an alkyl group or an 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 the compound in which the alkoxymethyl group or acyloxymethyl group is directly substituted with an aromatic group include compounds of the following general formula.

[Formula 26]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an acid A group that is decomposed by the action and generates an alkali-soluble group (for example, a group that is desorbed by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ are each independently a hydrogen atom or a carbon number) represents an alkyl group of 1 to 4, and R ⁵ represents a group that is eliminated by the action of an acid.)).

R ₁₀₅ Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, and a+ d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

For R 5 in a group decomposed by the action of an acid to generate an alkali-soluble group, a group desorbed ^by the action of an acid, and a 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 ), and the like.

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 said alkyl group, a C1-C10 alkyl group is preferable, and a C1-C5 alkyl group is more preferable.

The alkyl group may be linear or branched.

As said cycloalkyl group, a C3-C12 cycloalkyl group is preferable, and a C3-C8 cycloalkyl group is more preferable.

The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

It is preferable that the said aryl group is a C6-C30 aromatic hydrocarbon group, and it is more preferable that it is a phenyl group.

As said aralkyl group, a C7-C20 aralkyl group is preferable, and a C7-C16 aralkyl group is more preferable.

The aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-described alkyl and aryl groups.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

Moreover, these groups may further have a well-known substituent within the range in which the effect of this invention is acquired.

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.

These groups are preferably tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups and the like. More preferably, it is a tertiary alkyl ester group and an acetal ester group.

As a compound which has an alkoxymethyl group, the following structures are specifically mentioned. Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds has been changed to an acyloxymethyl group. Although the following compounds are mentioned as a compound which has an alkoxymethyl group or acyloxymethyl in a molecule|numerator, It is not limited to these.

[Formula 27]

[Formula 28]

As the 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 viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted onto an aromatic ring or triazine ring is preferable.

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

Specific examples of the urea-based crosslinking agent include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxy Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril , trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated Glycoluril-based crosslinking agents such as glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril ;

urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea;

monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, di Ethylene urea-based crosslinking agents such as propoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea;

monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, propylene urea-based crosslinking agents such as dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;

1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazoli dinone etc. are mentioned.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, and monomethoxymethylated benzoguanamine. Namine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, Tetraethoxymethylated Benzoguanamine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine, Monobutoxymethylated Benzoguanamine, Dibu Toxymethylation benzoguanamine, tributoxymethylation benzoguanamine, tetrabutoxymethylation benzoguanamine, etc. are mentioned.

In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring). Compounds are also suitably used.

Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, Hydroxymethylbenzoic acid Hydroxymethylphenyl, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl) Dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylbenzoic acid methoxymethylphenyl, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl) Biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(tri Fluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3 ', 5,5'-tetrakis (methoxymethyl) -1,1'-biphenyl-4 , 4'-diol, etc. are mentioned.

Commercially available products may be used as other crosslinking agents, and suitable commercially available products include 46DMOC, 46DMOEP (above, manufactured by Asahi Yukizai Kogyo Co., Ltd.), 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 (above, made by Honshu Kagaku Kogyo), Nikarak ( (registered trademark, hereinafter the same) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (above, manufactured by Sanwa Chemical Co., Ltd.), etc. there is.

Moreover, it is also preferable that the resin composition of this invention contains at least 1 sort(s) of compound selected from the group which consists of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

-Epoxy compound (compound having an epoxy group)-

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in 1 molecule. Since the epoxy group undergoes a crosslinking reaction at 200°C or lower and no dehydration reaction resulting from the crosslinking occurs, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective in low-temperature hardening of the resin composition of this invention and suppression of curvature.

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

As an example of an epoxy compound, it is bisphenol-A epoxy resin; bisphenol F-type epoxy resin; Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as diglycidyl ether and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, 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) N-665-EXP-S, Epiclon (registered trademark) N-740 (above product names, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-20E, Rica Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, New Japan Rica Co., Ltd.), EP- 4003S, EP-4000S, EP-4088S, EP-3950S (above product names, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolide (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide (registered trademark) PB3600 (above product names, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000 -H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H , EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (above brand name, Nippon Kayaku Co., Ltd. product), etc. are mentioned. Moreover, the following compounds are also used suitably.

[Formula 29]

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

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

-Oxetane compound (compound having an oxetanyl group)-

As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, and the like. . As a specific example, Aron Oxetane series (eg, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be suitably used, and these may be used alone or in combination of two or more.

-Benzoxazine compound (compound having a benzoxazolyl group)-

The benzoxazine compound is preferable in that it does not generate degassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and suppresses occurrence of warpage by reducing heat shrinkage.

Preferable examples of the benzoxazine compound include P-d-type benzoxazine, F-a-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolak-type dihydrobenzene. An oxazine compound is mentioned. These may be used independently or may mix 2 or more types.

The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and preferably 1.0 to 15% by mass, based on the total solid content of the resin composition of the present invention. It is especially preferable that it is 10 mass %. Another crosslinking agent may contain only 1 type, and may contain 2 or more types. When 2 or more types of other crosslinking agents are contained, it is preferable that the sum total is the said range.

<Metal Adhesion Improver>

The resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, and the like. As the metal adhesion improving agent, a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, β-keto An ester compound, an amino compound, etc. are mentioned.

[Silane coupling agent]

As a silane coupling agent, the compound of Paragraph 0167 of International Publication No. 2015/199219, the compound of Paragraph 0062 of Unexamined-Japanese-Patent No. 2014-191002 - the compound of 0073, Paragraph 0063 of International Publication No. 2011/080992, for example The compound described in ~ 0071, the compound described in paragraphs 0060 to 0061 of Japanese Laid-open Patent Publication No. 2014-191252, the compound described in paragraphs 0045 to 0052 of Japanese Patent Laid-Open No. 2014-041264, and the paragraph 0055 of International Publication No. 2014/097594 A compound and Paragraph 0067 of Unexamined-Japanese-Patent No. 2018-173573 - the compound of 0078 are mentioned, These content is integrated in this specification. Moreover, it is also preferable to use 2 or more types of silane coupling agents different as Paragraph 0050 of Unexamined-Japanese-Patent No. 2011-128358 - 0058 describe. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Me represents a methyl group and Et represents an ethyl group.

[Formula 30]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl -3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mer Captopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic acid anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based adhesive aid]

Examples of aluminum-based adhesive aids include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Moreover, as other metal adhesion improving agents, the compound described in Paragraph 0046 of Unexamined-Japanese-Patent No. 2014-186186 - 0049, and the sulfide-type compound of Paragraph 0032 - 0043 of Unexamined-Japanese-Patent No. 2013-072935 can also be used, These content is incorporated herein.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. By using the above lower limit or more, the adhesion between the pattern and the metal layer becomes good, and by using the above upper limit or less, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be one type or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

<Migration inhibitor>

It is preferable that the resin composition of this invention further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.

The migration inhibitor is not particularly limited, but is a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring) compounds having thioureas and sulfanyl groups , hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole-based compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole; Tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP-A-2013-015701, the compound described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compound described in paragraph 0052 of JP-A-2011-059656, The compound of Paragraph 0114 of Unexamined-Japanese-Patent No. 2012-194520, 0116, and 0118, the compound of Paragraph 0166 of International Publication No. 2015/199219, etc. can be used, These content is integrated in this specification.

Specific examples of the migration inhibitor include the following compounds.

[Formula 31]

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, and more preferably 0.05 to 2.0% by mass, based on the total solid content of the resin composition of the present invention. It is more preferable that it is 0.1-1.0 mass %.

One type of migration inhibitor may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of migration inhibitors, it is preferable that the sum total is the said range.

<Polymerization inhibitor>

It is preferable that the resin composition of this invention contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic compounds, and metal compounds.

Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and p-tert-butylcateta Col, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6 -tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine , ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycoletherdiamine tetraacetic 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-sulfopropylamino)phenol, N-nitro Bovine-N-(1-naphthyl)hydroxyamineammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3- Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhyd Razil, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt and the like are suitably used. used Moreover, the polymerization inhibitor of Unexamined-Japanese-Patent No. 2015-127817, Paragraph 0060, and Paragraph 0031 of International Publication No. 2015/125469 - the compound of 0046 can also be used, The content is integrated in this specification.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and more preferably 0.02 to 15% by mass with respect to the total solid content of the resin composition of the present invention. And, it is more preferable that it is 0.05 to 10% by mass.

1 type of polymerization inhibitor may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of polymerization inhibitors, it is preferable that the sum total is the said range.

<Diffusion scavenger>

The resin composition of the present invention preferably contains an acid trapping agent in order to reduce the change in performance over time from exposure to heating. Here, the acid scavenger refers to a compound capable of trapping a generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable. And, secondary amines, tertiary amines, and ammonium salts are more preferable.

As the acid scavenger, a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or ether bond, and a hydroxyl group and/or ether bond aniline derivatives having When it has an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator. it is desirable

Examples of the acid trapping agent having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole.

As the acid trapping agent having a diazabicyclo structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1, 8-diazabicyclo[5,4,0]undec-7-ene etc. are mentioned. As the acid scavenger having an onium structure, tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide oxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. can be heard Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the acid trapping agent having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.

Examples of the acid trapping agent having a pyridine structure include pyridine and 4-methylpyridine. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. As an aniline derivative which has a hydroxyl group and/or ether bond, N,N-bis (hydroxyethyl) aniline etc. are mentioned.

Specific examples of preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethyl Amine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene) ), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N -Methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6 -Hexenediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2 -Dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazole zoline, aminomorpholine, aminoalkylmorpholine and the like.

These acid trapping agents may be used individually by 1 type, or may be used in combination of 2 or more types.

The composition according to the present invention may or may not contain a dust trapping agent, but when it is contained, the content of the dust trapping agent is usually 0.001 to 10% by mass based on the total solids of the composition, preferably. is 0.01 to 5% by mass.

The use ratio of the acid generator and the acid scavenger is preferably acid generator/sand scavenger (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more in terms of sensitivity and resolution, and preferably 300 or less in terms of suppression of a decrease in resolution due to thickening of the relief pattern with time from exposure to heat treatment. The acid generator/dispersion complexing agent (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

<Other additives>

The resin composition of the present invention may contain various additives, for example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, and antioxidants, as necessary, within the range where the effects of the present invention are obtained. , aggregation inhibitors, phenolic compounds, other high molecular compounds, plasticizers, and other auxiliary agents (eg, antifoaming agents, flame retardants, etc.) can be blended. By appropriately containing these components, properties such as membrane properties can be adjusted. These components are, for example, described in paragraph No. 0183 of Japanese Laid-open Patent Publication No. 2012-003225 (paragraph No. 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph No. 2008-250074 Reference can be made to descriptions of 0101 to 0104 and 0107 to 0109, the contents of which are incorporated herein by reference. When blending these additives, the total compounding amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔Surfactants〕

As surfactant, various surfactants, such as a fluorochemical surfactant, a silicone type surfactant, and a hydrocarbon type surfactant, can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, in the case of forming a film 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 lowered, the wettability to the surface to be coated is improved, and the applicability to the surface to be coated is reduced. It improves. For this reason, it is possible to more suitably form a film having a uniform thickness with little thickness unevenness.

Examples of the fluorine-based surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F143. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Fluorad FC430, copper FC431, copper FC171, Novec FC4430, copper FC4432 (above, manufactured by 3M Japan Co., Ltd.), West Front S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, East KH-40 ( As mentioned above, Asahi Glass Co., Ltd. product), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. are mentioned. The compound described in Paragraph 0015 of Unexamined-Japanese-Patent No. 2015-117327 - 0158, and Paragraph 0117 of Unexamined-Japanese-Patent No. 2011-132503 - the compound of 0132 can also be used for a fluorochemical surfactant, The content of these is integrated in this specification. . A block polymer can also be used as a fluorochemical surfactant, and as a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example, These content is integrated in this specification.

The fluorine-based surfactant is a (meth)acrylate compound having 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group). ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 32]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

As the fluorochemical surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain may be used as the fluorochemical surfactant. As a specific example, Paragraph 0050 of Unexamined-Japanese-Patent No. 2010-164965 - 0090 and Paragraph 0289 - the compound of 0295 are mentioned, This content is integrated in this specification. Moreover, as a commercial item, DIC Corporation Megafac RS-101, RS-102, RS-718K etc. are mentioned, for example.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 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 liquid saving, and has good solubility in the composition.

As the silicone surfactant, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) product), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Co., Ltd.), KP-341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) ) agent), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

Examples of hydrocarbon surfactants include Pionin A-76, New Cargen 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 (above, Takemoto Yushi Co., Ltd.), etc. are mentioned.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , sorbitan fatty acid ester, etc. are exemplified. As commercially available products, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 ( Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (made by Wako Junyaku Kogyo Co., Ltd.), Pionein D-6112, D-6112-W, D-6315 (Yushi Takemoto) Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (Nisshin Chemical Co., Ltd. product), etc. are mentioned.

As the cationic surfactant, specifically, organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth)acrylic acid-based (co)polymer Poly Flo No. 75, no. 77, no. 90, no. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. are mentioned.

Specifically as anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), Sandet BL (made by Sanyo Kasei Co., Ltd.), etc. are mentioned.

Surfactant may use only 1 type, and may combine 2 or more types.

The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher Fatty Acid Derivatives]

To the resin composition of the present invention, in order to prevent inhibition of polymerization due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added and unevenly distributed on the surface of the resin composition of the present invention during drying after application. .

Moreover, as a higher fatty acid derivative, the compound of Paragraph 0155 of International Publication No. 2015/199219 can also be used, and this content is integrated 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 with respect to the total solid content of the resin composition of the present invention. 1 type of higher fatty acid derivative may be sufficient as it, and 2 or more types may be sufficient as it. When two or more types of higher fatty acid derivatives are used, it is preferable that the total is within the above range.

[Thermal polymerization initiator]

The resin composition of the present invention may contain a thermal polymerization initiator, and particularly may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound. Since the polymerization reaction of resin and a polymeric compound can also advance by adding a thermal radical polymerization initiator, solvent resistance can be improved more. In addition, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

As a thermal radical polymerization initiator, specifically, the compound described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned, This content is integrated in this specification.

When a thermal polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass with respect to the total solid content of the resin composition of the present invention. is mass %. The thermal polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of thermal polymerization initiators, it is preferable that the total amount is the said range.

[Inorganic Particles]

The resin composition of the present invention may also contain inorganic fine particles. Specific examples of 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 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

The average particle diameter of the fine particles is a primary particle diameter and is also a volume average particle diameter. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

When the above measurement is difficult, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[Ultraviolet rays absorber]

The composition of the present invention may contain a ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type, and triazine type can be used.

Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydride Roxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxy benzophenone, 2,4-dihydroxy benzophenone, 2-hydroxy-4-octoxy benzophenone, etc. are mentioned. In addition, 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-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole azoles, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and the like. Further, as an example of the triazine-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di Methylphenyl) -1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. Mono (hydroxyphenyl) triazine compounds of; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3 -Methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6 bis(hydroxyphenyl)triazine compounds such as -(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2- Hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]- and tris(hydroxyphenyl)triazine compounds such as 1,3,5-triazine.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types.

The composition of the present invention may or may not contain a ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.01 mass % or more and 0.1 mass % or less.

[organic titanium compound]

The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of organic titanium compounds are shown in I) to VII) below:

I) Titanium chelate compound: Especially, the titanium chelate compound which has 2 or more alkoxy groups is more preferable at the point from which the storage stability of a resin composition is favorable and a favorable curing pattern is obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-phen theindionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2] ,2-(allyloxymethyl)butoxide}] and the like.

III) titanocene compounds: eg pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl ) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

IV) Monoalkoxy titanium compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate and the like.

VII) Titanate coupling agent: For example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the viewpoint that the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound, which exhibits better chemical resistance. preferred in In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro Rho-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When blending an organic titanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, favorable heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, elongation characteristics of the film after curing and adhesion to a metal material can be improved. As an antioxidant, a phenol 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. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. As the phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) oxy]ethyl]amine, phosphorous acid ethylbis(2,4-di-tert-butyl-6-methylphenyl), and the like. As a commercial item of an antioxidant, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, for example, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (above, made by ADEKA Co., Ltd.), etc. are mentioned. Moreover, the antioxidant can also use the compound of Paragraph No. 0023 of Unexamined-Japanese-Patent No. 6268967 - 0048, The content of this is integrated in this specification.

Moreover, the composition of this invention may contain a latent antioxidant as needed.

As the latent antioxidant, the site functioning as an antioxidant is a compound protected by a protecting group, and the protecting group is released by heating at 100 to 250° C. or heating at 80 to 200° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. As a latent antioxidant, the compound of international publication 2014/021023, international publication 2017/030005, and Unexamined-Japanese-Patent No. 2017-008219 is mentioned, The content of this is integrated in this specification. As a commercial item of a latent antioxidant, Adeka Akles GPA-5001 (made by ADEKA Corporation) etc. are mentioned.

Examples of preferable antioxidants include compounds represented by 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and Formula (3).

[Formula 33]

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

The compound represented by formula (3) suppresses oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust-preventive effect on the metal material.

Since it can act simultaneously on the resin and the metal material, k is more preferably an integer of 2 to 4. As R7, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, - NH-, -NHNH-, what combined them, etc. are mentioned, You may have a substituent further. Among these, from the viewpoint of solubility in a developing solution and metal adhesion, those having an alkyl ether group and -NH- are preferable, and -NH- is more preferable from the viewpoint of interaction with resin and metal adhesion due to metal complexation. .

Although the following are mentioned as an example of the compound represented by General formula (3), It is not limited to the following structure.

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 parts by mass or more, the effect of improving the elongation properties and adhesion to metal materials is easily obtained even in a high-temperature, high-humidity environment, and by setting it to 10 parts by mass or less, for example, by interaction with the photosensitive agent, The sensitivity of the composition is improved. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that those total amounts become the said range.

[anti-agglomeration agent]

The resin composition of this embodiment may contain an aggregation inhibitor as needed. As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

In this invention, an aggregation inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain an aggregation inhibitor, but when it is included, the content of the aggregation inhibitor is preferably 0.01% by mass or more and 10% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.02 mass % or more and 5 mass % or less.

[phenolic compound]

The resin composition of this embodiment may contain a phenolic compound as needed. As the phenolic compound, 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, Methylenetris-FR-CR, BisRS-26X (above, product name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F (above, brand name, Asahi Yukizai Kogyo Co., Ltd. product), etc. are mentioned.

In this invention, a phenol type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain a phenolic compound, but when it is included, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention and more preferably 0.02% by mass or more and 20% by mass or less.

[Other high molecular compounds]

Examples of other high molecular compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins, copolymers thereof, and the like. The other high molecular compound may be a modified body into which a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group has been introduced.

In the present invention, the other high molecular compounds may be used singly or in combination of two or more.

The composition of the present invention may or may not contain other high molecular compounds, but in the case where they are included, the content of the other high molecular compounds is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention. and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of 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 the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s are preferred, 2,000 mm ² /s to 10,000 mm ² /s are more preferred, and 2,500 mm ² /s to 8,000 ^{mm 2} /s are preferred. more preferable If it is the said range, it becomes easy to obtain a coating film with high uniformity. At 1,000 mm ² /s or less, it is difficult to apply to a film thickness required as, for example, an insulating film for rewiring, and at 12,000 mm ² /s or more, the shape of the coated surface may deteriorate.

<Restrictions on Materials Contained in Resin Composition>

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. At 2.0% or more, there is a possibility that the storage stability of the resin composition is impaired.

As a method of maintaining the content of water, adjustment of humidity in storage conditions, reduction of the porosity of the container at the time of storage, etc. are mentioned.

From an insulating viewpoint, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When a plurality of metals are included, it is preferable that the sum of these metals is within the above range.

In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention, or a raw material constituting the resin composition of the present invention For example, a method of performing filter filtration on the substrate, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible is exemplified.

In the resin composition of the present invention, considering the use as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. more preferable Especially, as for what exists in the state of a halogen ion, less than 5 mass ppm is preferable, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is still more preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively is within the above range.

As a method of adjusting the content of halogen atoms, ion exchange treatment or the like is preferably used.

A conventionally well-known container can be used as a container for the resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multi-layered bottle in which the inner wall of the container is made of 6 types of 6-layer resin, and a bottle in which 6 types of resin are used in a 7-layer structure It is also preferable to use As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<cured product of resin composition>

By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.

The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

Curing of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and more preferably in the range of 170°C to 350°C. What is within the range is particularly preferred. The shape of the cured product of the resin composition is not particularly limited, and may be selected according to the application, such as a film shape, a rod shape, a spherical shape, or a pellet shape. In this invention, it is preferable that this hardened|cured material is film-like. In addition, by pattern processing of the resin composition, according to the application, such as formation of a protective film on the wall surface, formation of via holes for conduction, adjustment of impedance, capacitance or internal stress, imparting a heat dissipation function, The shape of this cured product can also be selected. It is preferable that the film thickness of this hardened|cured material (film|membrane consisting of hardened|cured material) is 0.5 micrometer or more and 150 micrometer or less.

The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated from the following formula.

Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

<Characteristics of cured product of resin composition>

The imidation reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If less than 70%, there is a possibility that the mechanical properties of the cured product are inferior.

The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.

The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

<Preparation of resin composition>

The resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and a conventionally known method can be used.

For the mixing, mixing by stirring blades, mixing by a ball mill, mixing by rotating the tank itself, or the like can be employed.

The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the resin composition of the present invention. As for the filter hole diameter, the aspect which is 5 micrometers or less is mentioned, for example, 1 micrometer or less is preferable, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene). As the filter, one previously washed with an organic solvent may be used. In the filter filtration process, you may connect and use multiple types of filters in series or parallel. In the case of using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. As a connection aspect, the aspect which connected the HDPE filter with a pore diameter of 1 micrometer as a 1st stage|stage, and the HDPE filter with a pore diameter of 0.2 micrometer as a 2nd stage|stage was connected in series, for example. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may perform filtration by pressurizing. In the case of filtering by pressurization, the pressurized pressure may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.05 MPa or more 0.5 MPa or less is more preferable.

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

After filtration using a filter, the resin composition filled in the bottle may be further subjected to a step of degassing under reduced pressure.

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are based on mass unless otherwise specified.

<Synthesis Example 1: Synthesis of Polymer P-1>

155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask with a capacity of 2 liters, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After completion of heat generation by the reaction, the mixture was allowed to cool to room temperature and left still for further 16 hours.

Next, under ice-cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Further, after stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. A precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethyl alcohol to produce a precipitate composed of a crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polymer P-1.

It was 20,000 as a result of measuring the weight average molecular weight (Mw) of this polymer P-1.

<Synthesis Example 2: Synthesis of Polymer P-2>

In Synthesis Example 1, the method described in Synthesis Example 1 except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. Polymer P-2 was obtained by reacting in the same manner as above.

It was 22,000 as a result of measuring the weight average molecular weight (Mw) of this polymer P-2.

<Synthesis Example 3: Synthesis of Polymer P-3>

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (4,4'-oxydiphthalic acid dried at 140 ° C for 12 hours) and 18.6 g (129 mmol) of 2-hydroxyethyl meta A mixture of acrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether), stirring at a temperature of 60 ° C. for 18 hours, 4,4 A diester of '-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to -10 °C and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at -10 ± 4 °C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Subsequently, a solution in which 11.08 g (58.7 mmol) of 4,4'-oxydianiline was dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23°C over 20 minutes. The reaction mixture was then stirred overnight at room temperature. Then, the polyimide precursor was precipitated by adding 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 collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45°C for 3 days under reduced pressure to obtain polymer P-3.

It was 18,000 as a result of measuring the weight average molecular weight (Mw) of this polymer P-3.

<Synthesis Example 4: Synthesis of Polymer P-4>

Into a flask equipped with a stirrer, thermometer, dropping funnel, and nitrogen inlet tube, 100.12 parts (0.5 mole) of 4,4'-diaminodiphenyl ether and 736 parts of N-methyl-2-pyrrolidone were introduced, and nitrogen gas was introduced. After stirring and dissolving at room temperature in an atmosphere, it cooled. Subsequently, 128.9 parts (0.4 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetra 42.65 parts (0.1 mol) of methyldisiloxane dianhydride and 50.4 parts of N-methyl-2-pyrrolidone were introduced, reacted under a nitrogen gas atmosphere at a reaction temperature of 30° C. It heated at °C for 20 hours to obtain a polyimide precursor. Next, 38.79 parts (0.25 mol) of isocyanate methacrylate was added to the obtained polyimide precursor at a reaction temperature of 35°C from a dropping funnel, followed by stirring for 10 hours to obtain polymer P-4.

<Examples and Comparative Examples>

In each Example, each photosensitive resin composition was obtained by mixing the components described in the table below, respectively. Moreover, in the comparative example, the components described in the table below were mixed to obtain a composition for comparison.

Specifically, the content of the components described in the table was set to the amount described in "parts by mass" in the table. In addition, in each composition, the content of the solvent was such that the solid content concentration of the composition was the value described in the table.

The obtained photosensitive resin composition and the composition for comparison were filtered under pressure through a filter made of polytetrafluoroethylene having a filter hole diameter of 0.8 μm.

In addition, in the table|surface, description of "-" shows that the composition does not contain the component concerned.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

The detail of each component described in the table|surface is as follows.

〔profit〕

P-1 to P-4: P-1 to P-4 synthesized above

[Radical Crosslinking Agent]

M-1: tetraethylene glycol dimethacrylate

M-2: tetraethylene glycol diacrylate

[Photoinitiator]

・I-1: Irgacure OXE-01 (manufactured by BASF)

I-2: 3,5-bis (4-diethylaminobenzylidene) -1-methyl-4-azacyclohexanone

・I-3: Irgacure 784 (manufactured by BASF)

[base generator]

・A-1: WPBG-140 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[Polymerization inhibitor]

B-1: 4-methoxyphenol

B-2: 2-nitroso-1-naphthol

[Silane coupling agent]

C-1: KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.)

C-2: N- (3- (triethoxysilyl) propyl) phthalamide acid

C-3: Benzophenone-3,3'-bis(N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic acid

[migration inhibitor]

D-1: tetrazole

〔additive〕

J-1: N-phenyldiethanolamine

J-2: N- (4-chlorophenyl) glycine

〔solvent〕

NMP: N-methyl-2-pyrrolidone

EL: ethyl lactate

GBL: γ-butyrolactone

DMSO: dimethyl sulfoxide

In the table, the description in the "ratio" column indicates the content (% by mass) of each solvent relative to the total mass of the solvent.

(evaluation)

<Evaluation of elongation at break>

In each Example and Comparative Example, each photosensitive resin composition or each comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100° C. for 5 minutes to form a photosensitive resin composition layer having a uniform thickness of 20 μm on the silicon wafer.

The photosensitive resin composition layer on the silicon wafer was exposed in a pattern (10 mm×50 mm) using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm and an exposure energy of 500 mJ/cm ² using a photomask.

After exposure, a developer prepared by mixing the "solvent" and "base" described in the "developer" column in the table in parts by mass listed in the table is supplied to the photosensitive resin composition layer after exposure by the supply method described in the "supply method" column in the table. supplied, and treated with the rinsing liquid described in the table.

In the example described as a shower, the developing solution was supplied for 1 minute at 100 ml/min using a shower nozzle.

In the example described as puddle, 100 ml of developing solution was supplied with a straight nozzle, and puddle development was repeated twice.

After the treatment, the exposed photosensitive resin composition (resin layer) was heated under a nitrogen atmosphere at a heating rate of 10°C/min to reach the temperature described in the "cure temperature (°C)" column in the table, and then "cure" in the table. The temperature was maintained for the time described in the column "Time (min)". The cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin layer (cured film).

The elongation at break of the resin layer (cured film) obtained above was determined as follows.

First, the resin layer (cured film) peeled off above was measured using a tensile tester (Tensilon) at a cross head speed of 300 mm/min in the long length (length) direction and width direction of the film, 25 ° C., 65% relative The elongation at break was measured in accordance with JIS-K6251:2017 under a humidity (RH) environment. The elongation at break in each of the longitudinal and transverse directions was measured 5 times each. The arithmetic average value of the total 10 measurement results of the elongation at break in the longitudinal direction and the transverse direction was used as the index value for the elongation at break. The index value (%) was described in the "elongation at break" column in the table. The one where the numerical value of elongation at break is higher is preferable, and 55% or more is regarded as a pass.

In addition, the details of the abbreviation described in the column of “developer” or “rinse solution” are as follows.

NMP: N-methyl-2-pyrrolidone

PGMEA: propylene glycol monomethyl ether acetate

PGME: Propylene glycol methyl ether

TMAHaq: 25% by mass aqueous solution of tetramethylammonium hydroxide

<Evaluation of peeling defects (adhesion between layers)>

In each Example and Comparative Example, each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100° C. for 5 minutes to form a photosensitive resin composition layer having a uniform thickness described in the “film thickness (μm)” column on the silicon wafer. Then, the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm and an exposure energy of 500 mJ/cm ² , and the exposed photosensitive resin composition layer (resin layer), Shower development and rinsing were performed for 60 seconds with each developing solution to form a hole with a diameter of 10 μm. Then, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10 ° C./min, and after reaching the temperature described in “Cure temperature (° C.)” in the table, it was heated for the time described in “Cure time (min)” in the table. After cooling to room temperature, the same composition as the photosensitive resin composition or the composition for comparison was used again on the surface of the resin layer, and the procedure from application of the photosensitive resin composition to heating of the patterned film for 3 hours was followed in the same manner as above. This was carried out again to form a laminate 1 having two resin layers.

[Manufacture of laminate (2)]

On the surface of the layered product (1) obtained above, by using the same composition as the photosensitive resin composition used in the production of the layered product (1) or the composition for comparison, by performing the same procedure as in the production of the layered product (1) again, A layered product 2 having four resin layers was produced.

[Manufacture of laminate (3)]

In each Example and Comparative Example, each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100° C. for 5 minutes to form a photosensitive resin composition layer having a uniform thickness described in the “film thickness (μm)” column on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed to light with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was developed for 60 seconds with each developer. , forming a hole with a diameter of 10 μm. Then, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10 ° C./min, and after reaching the temperature described in “Cure temperature (° C.)” in the table, it was heated for the time described in “Cure time (min)” in the table. After cooling to room temperature, a copper foil layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. In addition, the same photosensitive resin composition or comparative composition is used again on the surface of the metal layer and the photosensitive resin composition layer, and the procedure from application of the photosensitive resin composition to heating of the patterned film for 3 hours is carried out again in the same manner as above. Thus, a laminate 3 comprising a resin layer/metal layer/resin layer was produced.

[Manufacture of laminate (4)]

On the surface of the laminate 3, by the same method as in the laminate 3, a copper foil layer (metal layer) and a resin layer are alternately prepared, and a resin layer/metal layer/resin layer/metal layer/resin layer/ A laminate 4 composed of a metal layer/resin layer was produced.

[Evaluation of peeling defects (after heat treatment)]

Each laminate obtained above was heated at 180°C in air for 500 hours. Thereafter, with respect to the resin layer surface of each laminate, a portion in contact with the resin layer and a portion in contact with the metal layer were cut out so as to have a width of 5 mm in the vertical direction, respectively. The cut cross section was observed, and the presence or absence of peeling between the resin layer/resin layer and between the metal layer/resin layer in one cut piece was confirmed with an optical microscope. The occurrence of peeling was confirmed by the number of pieces in the whole, regardless of whether it was peeling between resin layers/resin layers or between metal layers/resin layers. The evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the "lamination reliability" column of the table. It shows that it has excellent adhesiveness, so that there is little generation|occurrence|production of peeling, and it becomes a preferable result.

-Evaluation results-

A: No occurrence of peeling

B: 1 to 2 occurrences of peeling

C: 3 to 5 occurrences of peeling

D: 6 or more occurrences of peeling

In the method for producing the cured product according to Comparative Example 1 or Comparative Example 2, a developer containing no base was used. In such an example, it turns out that the breaking elongation of the cured film obtained is inferior.

<Example 101>

The photosensitive resin composition used in Example 1 was applied layer by layer to the surface of the copper foil layer of the resin substrate having the copper foil layer formed thereon by a spin coating method, dried at 100°C for 4 minutes, and the photosensitive resin composition having a film thickness of 20 μm. After forming the layer, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it heated at 100 degreeC for 4 minutes. After the heating, it was developed with the developer used in Example 1 and rinsed with the rinse solution used in Example 1 to obtain a layer pattern.

Then, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10°C/min, and after reaching 180°C, the layer was cured by holding for 120 minutes to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer was excellent in insulating properties.

In addition, as a result of manufacturing electronic devices using these interlayer insulating films for redistribution layers, it was confirmed that they operated without problems.

Claims (9)

A film formation step of forming a film by applying a photosensitive resin composition containing a polyimide precursor having a repeating unit represented by the following formula (2) and a photopolymerization initiator onto a substrate;
An exposure step of selectively exposing the film to light;
A developing step of forming a pattern by developing the film after exposure with a developing solution containing at least one compound selected from the group consisting of a base and a base generator; and
A heating step of heating the pattern obtained by the development,
The method for producing a cured product, wherein the content of water with respect to the total mass of the developer is 50% by mass or less.
[Formula 1]

In Formula (2), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹³ and R ¹¹⁴ each independently represent a monovalent organic group, and R ¹¹⁵ represent a tetravalent organic group , R ¹¹¹ represents a divalent organic group. The method of claim 1,
The method for producing a cured product, wherein the developing solution contains an organic base as the base. According to claim 1 or claim 2,
The heating step promotes imidation of the polyimide precursor in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator by heating. A process for producing a cured product. The method according to any one of claims 1 to 3,
The manufacturing method of the hardened|cured material whose heating temperature in the said heating process is 120-230 degreeC. The method according to any one of claims 1 to 4,
The method for producing a cured product, wherein the developing step is a step of supplying the developing solution to the film after exposure by showering or continuously supplying the developing solution. The method according to any one of claims 1 to 5,
The method for producing a cured product, wherein the development in the development step is negative development. The manufacturing method of the laminated body which repeats the manufacturing method of the hardened|cured material in any one of Claims 1-6 multiple times. The method of claim 7,
The manufacturing method of the laminated body which further includes the metal layer formation process of forming a metal layer on hardened|cured material between the said manufacturing method of hardened|cured material performed multiple times. The manufacturing method of an electronic device including the manufacturing method of the hardened|cured material in any one of Claims 1-6, or the manufacturing method of the laminated body of Claim 7 or Claim 8.