KR20190027881A - METHOD FOR PRODUCING LAMINATE AND METHOD FOR MANUFACTURING ELECTRONIC DEVICE - Google Patents

Abstract

A method of manufacturing a laminate excellent in adhesion and a method of manufacturing an electronic device are provided. A step of forming a photosensitive resin composition layer by applying a photosensitive resin composition containing a resin such as a polyimide precursor and a photopolymerization initiator on a support, an exposure step of exposing the photosensitive resin composition layer in a pattern form, , A developing step of developing the photosensitive resin composition layer to form a pattern, a heating step of heating the pattern, and a metal layer forming step of forming a metal layer on the pattern after heating. In the step of forming the photosensitive resin composition layer and the step of exposing , At least one of between the exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step, the surface temperature is maintained for at least 5 minutes .

Description

METHOD FOR PRODUCING LAMINATE AND METHOD FOR MANUFACTURING ELECTRONIC DEVICE

The present invention relates to a method of manufacturing a laminate and a method of manufacturing an electronic device.

Resins such as polyimide and polybenzoxazole are excellent in heat resistance and insulation properties and are thus used in insulating layers of electronic devices and the like. Since polyimide and polybenzoxazole are low in solubility in solvents, they are applied to a support or the like in the form of a precursor before the cyclization reaction (polyimide precursor or polybenzoxazole precursor) and then heated to form a polyimide precursor or polybenzoxazine And a cured film is formed by cyclizing the sol precursor.

For example, Patent Documents 1 and 2 describe the production of a patterned cured film using a photosensitive resin composition comprising a polyimide precursor and a photopolymerization initiator.

Patent Document 1: JP-A-2011-191749 Patent Document 2: JP-A-2014-201695

The inventors of the present invention have studied a photosensitive resin composition comprising a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator. As a result, it has been found that a photosensitive resin composition comprising these resins It has been found that the film formed by using the film may have insufficient adhesion with the support, the metal layer or the like.

Therefore, an object of the present invention is to provide a method of manufacturing a laminate excellent in adhesion and a method of manufacturing an electronic device.

As a result of the inventors' investigation under the above-mentioned problems, it has been found that a film formed by using a photosensitive resin composition comprising a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole and a photopolymerization initiator, , It tends to require time until the properties of the film are stabilized. It has been found that a laminate excellent in adhesion can be produced by providing a predetermined storage step in any one of the below-described steps, and has solved the above problems. The present invention provides the following.

≪ 1 > A photosensitive resin composition for forming a photosensitive resin composition layer by applying a photosensitive resin composition comprising a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a resin selected from polybenzoxazole, and a photopolymerization initiator to a support A layer forming step,

An exposure step of exposing the photosensitive resin composition layer in a pattern shape,

A developing step of developing the photosensitive resin composition layer to form a pattern,

A heating step of heating the pattern,

And a metal layer forming step of forming a metal layer on the pattern after heating,

At least one of the steps of forming the photosensitive resin composition layer and the exposure step, between the exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step, , And then carrying out a preservation step for preservation in that state for 5 minutes or more.

&Lt; 2 > A method for producing a laminate according to < 1 >, wherein a preservation step is carried out between an exposure step and a development step.

&Lt; 3 > A method for producing a laminate according to < 2 >, wherein the preservation step performed between the exposure step and the development step satisfies the following formula:

^{5≤t1 <(10 -. 0.036 ×} T1 +12 3) × 60

T1 is an average surface temperature in the preservation step carried out between the exposure step and the developing step, and the unit is K; t1 is the time of the storage step performed between the exposure step and the developing step, and the unit is minute.

&Lt; 4 > A method for producing a laminate according to any one of < 1 > to < 3 >, wherein a preservation step is performed between a photosensitive resin composition layer forming step and an exposure step.

&Lt; 5 > A method for producing a laminate according to < 4 >, wherein the preservation step performed between the photosensitive resin composition layer forming step and the exposure step satisfies the following formula:

^{5≤t2 <(10 -. 0.031 ×} T2 +10 7) × 60

T2 is an average surface temperature in the storage step performed between the photosensitive resin composition layer forming step and the exposure step, and the unit is K; t2 is the time of the preservation step performed between the photosensitive resin composition layer forming step and the exposure step, and the unit is minutes.

<6> The method for producing a laminate according to any one of <1> to <5>, wherein a preservation step is carried out between the developing step and the heating step.

<7> The method for producing a laminate according to <6>, wherein the preservation step performed between the developing step and the heating step satisfies the following formula:

T3 < (10 ^{- 0.02 x T3 +} 8.0) x 60

T3 is the average surface temperature in the storage step carried out between the developing step and the heating step, and the unit is K; t3 is the time of the storage step performed between the developing step and the heating step, and the unit is minute.

<8> A method for producing a laminate according to any one of <1> to <7>, wherein a preservation step is performed between a heating step and a metal layer forming step.

<9> The photosensitive resin composition according to any one of <1> to <13>, wherein the resin in the photosensitive resin composition is a polyimide precursor, the polyimide precursor contains a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than a polyimide precursor. Wherein the laminated body is a laminated body.

<10> The method for producing a laminate according to any one of <1> to <9>, wherein the polyimide precursor comprises a repeating unit represented by the following formula (1):

Equation (1)

[Chemical Formula 1]

In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group.

<11> A process for producing a laminate according to <10>, wherein at least one of R ²³ and R ²⁴ in the formula (1) contains a radically polymerizable group.

<12> The process for producing a laminate according to <10> or <11>, wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring.

A step of forming a photosensitive resin composition layer, an exposure step, a development step, a heating step and a metal layer formation step are carried out in this order on the pattern after the metal layer formation step. Between the photosensitive resin composition layer formation step and the exposure step, The method according to any one of < 1 > to < 12 >, wherein at least one of the series of cycles for carrying out the preservation step is carried out in at least one of a heating step and a heating step, Wherein the laminate is a laminate.

&Lt; 14 > A production method of a laminate according to any one of < 1 > to < 13 >, which is a production method of a laminate of a multilayer wiring structure.

<15> A photosensitive resin composition for forming a photosensitive resin composition layer by applying on a support a photosensitive resin composition comprising a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a resin selected from polybenzoxazole and a photopolymerization initiator A layer forming step,

An exposure step of exposing the photosensitive resin composition layer in a pattern shape,

A developing step of developing the photosensitive resin composition layer to form a pattern,

A heating step of heating the pattern,

And a metal layer forming step of forming a metal layer on the pattern after heating,

At least one of the steps of forming the photosensitive resin composition layer and the exposure step, between the exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step, And then performing a preservation step of preserving the state for 5 minutes or longer.

&Lt; 16 > A method for manufacturing an electronic device according to < 15 >, wherein a plurality of electronic devices are manufactured under the condition of the same storage step.

According to the present invention, it becomes possible to provide a method of manufacturing a laminate excellent in adhesion and a method of manufacturing an electronic device.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a configuration of an embodiment of a laminate. Fig.
2 is a schematic view showing a configuration of an embodiment of an electronic device.

The following description of constituent elements in the present invention is based on a representative embodiment of the present invention, but the present invention is not limited to such embodiments.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes a group having a substituent and a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, the term " exposure " includes not only exposure using light but also drawing using particle beams such as electron beam and ion beam, unless otherwise described. The light used for exposure generally includes an active ray or radiation such as a line spectrum of a mercury lamp, far ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X ray, or electron ray.

In the present specification, the numerical value range indicated by using " ~ " means a range including numerical values before and after "~" as a lower limit value and an upper limit value.

As used herein, "(meth) acrylate" refers to either or both of "acrylate" and "methacrylate", and "(meth) allyl" (Meth) acryloyl " refers to both " acryloyl " and " methacryloyl "Quot; or " methacryloyl "

In the present specification, the term " process " is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

In the present specification, the solid concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition. The solid content concentration refers to the concentration at 25 캜 unless otherwise specified.

In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene reduced values according to Gel Permeation Chromatography (GPC) measurement unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION) as a column, a guard column HZ-L, TSKgel Super HZM- M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, THF (tetrahydrofuran) is used as the eluent. It is assumed that a detector of wavelength 254 nm of UV ray (ultraviolet ray) is used unless otherwise described.

&Lt; Method for producing laminate >

The method for producing a laminate of the present invention is a method for producing a laminate by applying a photosensitive resin composition comprising a polyimide precursor, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator to a support to form a photosensitive resin composition A step of forming a photosensitive resin composition layer,

An exposure step of exposing the photosensitive resin composition layer in a pattern shape,

A developing step of developing the photosensitive resin composition layer to form a pattern,

A heating step of heating the pattern,

And a metal layer forming step of forming a metal layer on the pattern after heating,

At least one of the steps of forming the photosensitive resin composition layer and the exposure step, between the exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step, , And then performing a preservation step of preserving it for 5 minutes or more in this state.

According to the present invention, a laminate having excellent adhesion can be formed. The reason why such an effect is obtained is presumed to be as follows. The film formed using the above-described resin and the photosensitive resin composition containing the photopolymerization initiator tends to require time until the property of the film is stabilized. When the subsequent process (for example, after the photosensitive resin composition layer forming process and subsequent exposure process) is performed in a state in which the property of the film is not stabilized, a region where the reaction locally progresses in the film And stress is locally applied to the film. On the other hand, according to the present invention, it is possible to stabilize the property of the film and to carry out the processing of the next step in a state in which residual stress of the film is relaxed by providing the above-mentioned preservation step during any one of the above- . As a result, it is presumed that a laminate excellent in adhesion can be produced.

When the above-mentioned resin in the photosensitive resin composition is a polyimide precursor and the polyimide precursor contains a radically polymerizable group or a photosensitive resin composition containing a radically polymerizable compound other than the above-described polyimide precursor Particularly, the effect of the present invention is remarkable. Although the detailed reason is unknown, when a photosensitive resin containing such a radically polymerizable component (a polyimide precursor having a radically polymerizable group, a radically polymerizable compound other than a polyimide precursor) is used, in the exposure process and the development process, A pattern is formed using a crosslinking reaction by radical polymerization of a radical polymerizing component and the resulting pattern is heated at a high temperature in a heating step to cause an imidization reaction to form a film with high heat resistance and high insulation. When the photosensitive composition containing the above-described radically polymerizable component is used as described above, the reaction is complicated because the reaction is multistep. However, by providing the above-mentioned preservation step, the microscopic state of the film can be stabilized, It is presumed that a laminate excellent in adhesion can be produced.

Hereinafter, each step in the method for producing a laminate of the present invention will be described.

(Step of forming a photosensitive resin composition layer)

The method for producing a laminate of the present invention includes a step of forming a photosensitive resin composition layer in which a photosensitive resin composition is applied on a support to form a photosensitive resin composition layer. The photosensitive resin composition will be described later.

The kind of the support can be appropriately determined depending on the application. Examples thereof include an inorganic substrate, a resin substrate, and a resin composite substrate. Examples of the inorganic substrate include glass substrates, quartz substrates, silicon substrates, silicon nitride (silicon nitride) substrates, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper, have. As the resin substrate, it is possible to use, for example, polystyrene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycolcarbonate, polyamide , Fluoropolymers such as polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, A substrate made of synthetic resin such as silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic ether, maleimide, olefin, cellulose, and episulfide compound. These substrates are rarely used in the above-described form, and a multi-layered laminate structure such as a thin film transistor (TFT) element is usually formed depending on the shape of the final product. When a photosensitive resin composition layer is additionally formed on the surface of the photosensitive resin composition layer or the surface of the metal layer, the photosensitive resin composition layer or the metal layer serves as the support.

As a method of applying the photosensitive resin composition to the support, application is preferred. Examples of specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and ink-jet coating. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, the spin coat method is more preferable. In the case of the spin coating method, for example, the spin coating can be applied at a rotation speed of 500 to 2000 rpm for 10 seconds to 1 minute.

The thickness of the photosensitive resin composition layer is preferably such that the film thickness after exposure is 0.1 to 100 占 퐉, more preferably 1 to 50 占 퐉. The thickness of the formed photosensitive resin composition layer is not necessarily uniform. For example, when a photosensitive resin composition layer is formed on a surface having irregularities, a photosensitive resin composition layer having a different thickness may be formed.

In the step of forming the photosensitive resin composition layer, the photosensitive resin composition layer formed on the support may be dried. The drying temperature is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, and even more preferably 90 to 110 ° C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, and even more preferably 3 to 7 minutes. The drying treatment is a step different from the preservation step of the present invention.

(Exposure step)

The method for producing a laminate of the present invention includes an exposure step for exposing the photosensitive resin composition layer in a pattern shape. Exposure, it is specifically determined that can cure the photosensitive resin composition, but for example, it is preferable that irradiation with 100 ~ 10000mJ / cm ² as an exposure energy conversion at a wavelength of 365nm, and the irradiation to the 200 ~ 8000mJ / cm ² . The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and preferably 240 to 550 nm.

(Developing step)

The method for producing a laminate of the present invention includes a developing step of developing the photosensitive resin composition layer to form a pattern on the exposed photosensitive resin composition layer. The development is carried out using a developing solution. The developing solution can be used without particular limitation. Solvents are preferred. Examples of the solvent used in the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. For the details of these, there may be mentioned the solvents described in the column of the resin composition to be described later.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, Cyclohexanone, cyclopentanone, gamma -butyrolactone, dimethylsulfoxide, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred, Cyclopentanone, and gamma -butyrolactone are more preferable.

The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not specifically defined, but can be 20 to 40 占 폚. After the treatment using the developing solution, rinsing may be further performed. The rinsing is preferably performed with a solvent different from the developing solution. For example, rinsing can be performed using a solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

(Heating process)

The method for producing a laminate of the present invention includes a heating step of heating a pattern (resin layer) obtained by a developing step. In the heating process, the cyclization reaction of the polyimide precursor or the like proceeds. In addition, curing of the unreacted radically polymerizable component proceeds. The maximum heating temperature (maximum temperature at the time of heating) is preferably 100 to 500 占 폚, more preferably 140 to 400 占 폚, and even more preferably 160 to 350 占 폚.

The heating is preferably carried out at a heating rate of 1 to 12 ° C / minute from a temperature of 20 to 150 ° C to a maximum heating temperature, more preferably 2 to 10 ° C / minute, and still more preferably 3 to 10 ° C / minute. The excessively volatilized amine can be prevented while securing a high productivity, and the temperature remaining at the obtained film can be relaxed by setting the rate of temperature increase to 2 DEG C / min or more.

The temperature at the start of heating is preferably 20 to 150 占 폚, more preferably 20 to 130 占 폚, and still more preferably 25 to 120 占 폚. The temperature at the start of heating refers to the heating temperature at the start of the step of heating up to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto a substrate and then dried, it is preferable to raise the temperature after the drying, for example, from a temperature 30 to 200 ° C lower than the boiling point of the solvent contained in the photosensitive resin composition .

The heating is preferably performed for 10 to 360 minutes after reaching the maximum heating temperature, more preferably for 20 to 300 minutes, and particularly preferably for 30 to 240 minutes.

The heating may be performed stepwise. For example, a process of raising the temperature from 25 ° C to 180 ° C by 3 ° C / minute, placing it at 180 ° C for 60 minutes, raising the temperature from 180 ° C to 200 ° C at 2 ° C / minute, and leaving it at 200 ° C for 120 minutes .

Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C / minute.

The heating process is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, in view of preventing the decomposition of the polyimide precursor or the like. The oxygen concentration is preferably 50 vol ppm or less, more preferably 20 vol ppm or less.

(Metal layer forming step)

The method for producing a laminate of the present invention includes a metal layer forming step of forming a metal layer on a pattern (resin layer) after heating. As the metal layer, existing metal species can be used without particular limitation. For example, copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten may be mentioned, and copper and aluminum are preferable, and copper is more preferable. The method of forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination thereof are conceivable. More specifically, a patterning method using a combination of sputtering, photolithography and etching, and a patterning method using a combination of photolithography and electrolytic plating can be given.

The thickness of the metal layer is preferably 0.1 to 50 mu m, more preferably 1 to 10 mu m in the thickest portion.

(Surface activation treatment process)

The method for producing a laminate of the present invention may include a surface activation treatment step of surface-activating at least a part of the metal layer and the photosensitive resin composition layer. The surface activation treatment may be performed on at least only a part of the metal layer or only at least a part of the photosensitive resin composition layer after the heating step and may be performed to at least part of both the metal layer and the photosensitive resin composition layer after the heating step do.

The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer may be formed after the surface activation treatment step is performed on the photosensitive resin composition layer after the heating step.

The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on a part or the whole of the region where the photosensitive resin composition layer is formed on the surface of the metal layer. By performing the surface activation treatment on the surface of the metal layer as described above, the adhesion with the photosensitive resin composition layer provided on the surface of the metal layer can be improved.

It is preferable that the surface activation treatment is also performed on a part or all of the photosensitive resin composition layer after the heating step. By performing the surface activation treatment on the surface of the photosensitive resin composition layer in this manner, the adhesion to the metal layer or the photosensitive resin composition layer provided on the surface subjected to the surface activation treatment can be improved.

As the surface activation treatment, various kinds of the raw material gas plasma processing (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixture gas, an argon / oxygen gas mixture and the like), corona discharge treatment, CF ₄ / O _2, NF ₃ / O _2, An organic material including a compound having at least one amino group and at least one thiol group after removal of the oxide film by etching treatment with SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment with ultraviolet (UV) ozone method, An immersion treatment with a surface treatment agent, and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen for a raw material gas is particularly preferable. For the corona discharge treatment, energy, 500 ~ 200000J / m ² are preferred, and more preferably 1000 to the ^{100000J / m 2, 10000 ~ 50000J} / m 2 is most preferred.

(Preservation process)

The method for producing a laminate of the present invention is characterized in that at least one of a photosensitive resin composition layer forming step and an exposure step, between an exposure step and a developing step, between a developing step and a heating step, and between a heating step and a metal layer forming step , A storage step is performed in which the surface temperature is maintained for 5 minutes or more after the temperature reaches a certain temperature. The above-described preservation step may be performed for each step, or the preservation step described above may be performed in only one of the steps. In the present invention, it is preferable to perform the above-described preservation step in at least one of the step of forming the photosensitive resin composition layer and the exposing step, the step of exposing and developing, and the step of developing and heating, It is more preferable to perform the preservation step during the developing process. By carrying out a preservation step between the exposure step and the developing step, the adhesion of the photosensitive resin composition layer can be further improved.

In the present invention, the term &quot; preservation step &quot; means a step of maintaining the surface temperature for 5 minutes or more after the surface temperature reaches a certain temperature. Here, the surface temperature means the surface temperature of a material to be processed such as a pattern (resin layer) formed by the photosensitive resin composition layer or the photosensitive resin composition layer.

In the present invention, the constant temperature in the preservation step does not mean any specific temperature, but may have a predetermined temperature range. The variation width (difference between the maximum value and the minimum value of the surface temperature of the object to be treated in the preservation step) is preferably 15 占 폚 or lower, more preferably 10 占 폚 or lower, and still more preferably 5 占 폚 or lower. When the fluctuation range of the surface temperature is within the above-mentioned range, it is easy to stabilize the property of the film and to easily produce a laminate having excellent adhesiveness.

In the present invention, the average surface temperature of the object to be treated in the preservation step is preferably -30 占 폚 or higher, more preferably 4 占 폚 or higher, more preferably 10 占 폚 or higher, and particularly preferably 20 占 폚 or higher. The upper limit is preferably 100 占 폚 or lower, more preferably 60 占 폚 or lower, still more preferably 45 占 폚 or lower, and particularly preferably 30 占 폚 or lower. In addition, the average surface temperature of the object to be treated means the average of the surface temperatures of the object to be treated per hour. The storage step is performed for 5 minutes or more.

When the preservation step (hereinafter, this preservation step is also referred to as a PED (Post Exposure Delay) step) is carried out between the exposure step and the development step, the PED step is preferably carried out under conditions satisfying the following formula.

^{5≤t1 <(10 -. 0.036 ×} T1 +12 3) × 60

T1 is the average surface temperature in the PED process and is in K; t1 is the time of the PED process and the unit is minutes.

The average surface temperature of the object to be treated in the PED process is preferably -30 to 60 占 폚, more preferably 4 to 45 占 폚, and more preferably 20 to 30 占 폚. The PED process is preferably performed for 5 to 720 minutes, more preferably 5 to 480 minutes, and more preferably 5 to 360 minutes. The variation range of the surface temperature of the object to be treated in the PED process is preferably 15 占 폚 or lower, more preferably 10 占 폚 or lower, still more preferably 5 占 폚 or lower.

When the preservation step (hereinafter, this preservation step is also referred to as a PCD (Post Coating Delay) step) is performed between the photosensitive resin composition layer forming step and the exposure step, the PCD step is preferably carried out under conditions satisfying the following formula.

^{5≤t2 <(10 -. 0.031 ×} T2 +10 7) × 60

T2 is the average surface temperature in the PCD process and is in K; t2 is the time of the PCD process and the unit is minutes.

The average surface temperature of the object to be treated in the PCD process is preferably -30 to 60 占 폚, more preferably 4 to 45 占 폚, and more preferably 20 to 30 占 폚. The PCD process is preferably performed for 5 to 360 minutes, more preferably 5 to 120 minutes, and more preferably 5 to 60 minutes. The variation range of the surface temperature of the object to be processed in the PCD process is preferably 15 占 폚 or lower, more preferably 10 占 폚 or lower, and still more preferably 5 占 폚 or lower.

When the preservation step (hereinafter, this preservation step is also referred to as a PDD (Post Developing Delay) step) is carried out between the developing step and the heating step, the PDD step is preferably carried out under conditions satisfying the following formula.

T3 < (10 ^{- 0.02 x T3 +} 8.0) x 60

T3 is the average surface temperature in the PDD process and is in K; t3 is the time of the PDD process and the unit is minutes.

The average surface temperature of the object to be processed in the PDD process is preferably 4 to 80 캜, more preferably 10 to 60 캜, and still more preferably 20 to 30 캜. The PDD process is preferably performed for 5 to 1200 minutes, more preferably 5 to 720 minutes, more preferably 5 to 600 minutes, and most preferably 5 to 300 minutes. The variation range of the surface temperature of the object to be processed in the PDD process is preferably 30 占 폚 or lower, more preferably 20 占 폚 or lower, and even more preferably 10 占 폚 or lower.

When the preservation step (hereinafter, this preservation step is also referred to as a PBD (Post Bake Delay) step) is carried out between the heating step and the metal layer forming step, the average surface temperature of the object to be treated in the PBD step is 4 to 100 占 폚 More preferably 10 to 80 占 폚, and still more preferably 20 to 60 占 폚. The PBD process is preferably performed for 5 to 2400 minutes, more preferably 5 to 1200 minutes, more preferably 5 to 900 minutes, and most preferably 5 to 600 minutes. The fluctuation range of the surface temperature of the object to be treated in the PBD process is preferably 60 占 폚 or lower, more preferably 45 占 폚 or lower, still more preferably 30 占 폚 or lower.

The method for producing a laminate of the present invention is characterized in that a step of forming a photosensitive resin composition layer, an exposure step, a developing step, a heating step and a metal layer forming step are carried out in this order on a pattern (resin layer) A series of cycles for carrying out the preservation step in at least one of the resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step It is also preferable to perform two or more cycles. The above-described cycle is preferably performed 2 to 7 times, more preferably 2 to 5 times. By doing so, a laminate of a multilayer wiring structure in which a plurality of resin layers and metal layers formed from a photosensitive resin composition layer are alternately stacked can be manufactured.

Further, by increasing the number of layers, peeling easily occurs at the interface between the metal layer and the resin layer, the interface between the resin layers, and the interface between the resin layer and the support. However, according to the method for producing a laminate of the present invention , Peeling in each layer is unlikely to occur even if the number of stacked layers is increased. Thus, the effect of the present invention is more remarkably obtained.

1 is a diagram showing an example of a multilayer structure of a multilayer interconnection structure. Reference numeral 500 in the figure denotes a laminate, reference numerals 201 to 204 denote a resin layer, and reference numerals 301 to 303 denote metal layers.

A desired pattern is formed on the resin layer 201. For example, this pattern can be formed by, for example, a negative type phenomenon. A metal layer 301 is formed on the surface of the resin layer 201. The metal layer 301 is formed so as to cover a part of the surface of the groove 401 formed in the resin layer 201.

On the metal layer 301, a resin layer 202 is formed. A desired pattern is formed in the resin layer 202, and a part of the metal layer 301 is exposed from the resin layer 202. A metal layer 302 is formed on the surface of the resin layer 202. The metal layer 302 is formed so as to cover a part of the surface of the groove 402 formed in the resin layer 202 and is electrically connected to the metal layer 301 exposed from the resin layer 202.

On the metal layer 302, a resin layer 203 is formed. A desired pattern is formed on the resin layer 203, and a part of the metal layer 302 is exposed from the resin layer 203. A metal layer 303 is formed on the surface of the resin layer 203. The metal layer 303 is formed so as to cover a part of the surface of the groove 403 formed in the resin layer 203 and is electrically connected to the metal layer 302 exposed from the resin layer 203.

On the metal layer 303, a resin layer 204 is formed. A desired pattern is formed on the resin layer 204, and a part of the metal layer 303 is exposed from the resin layer 204. 1, part of the metal layer 302 is also exposed from the resin layer 204. [

In this laminate, the resin layers 201 to 204 serve as insulating films, and the metal layers 301 to 303 function as wiring layers. Such a laminate can be preferably used as a rewiring layer in an electronic device.

&Lt; Photosensitive resin composition (resin composition) >

Next, the photosensitive resin composition (hereinafter also referred to as a resin composition) used in the method for producing a laminate of the present invention will be described.

<< Resin >>

The resin composition of the present invention includes a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and polybenzoxazole. When a polyimide precursor or a polybenzoxazole precursor is used as the resin, the property of the film tends to be less stable. Therefore, when a polyimide precursor or a polybenzoxazole precursor is used as the resin, the effect of the present invention is particularly remarkable. Among them, particularly when the polyimide precursor (preferably a polyimide precursor having a radically polymerizable group) is used as the resin, the effect of the present invention is more easily obtained.

The content of the resin in the resin composition is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, further preferably 60 to 99% by mass, more preferably 70 to 99% by mass based on the total solid content of the resin composition % Is particularly preferable.

The content of the polyimide precursor in the resin composition is preferably from 20 to 99% by mass, more preferably from 50 to 99% by mass, further preferably from 60 to 99% by mass, based on the total solid content of the resin composition , And particularly preferably 70 to 99 mass%.

The content of the polyimide precursor in the total mass of the resin contained in the resin composition is preferably 80 to 100 mass%, more preferably 90 to 100 mass%. It is preferable that the resin contained in the resin composition is substantially composed of only the polyimide precursor. The case where the resin contained in the resin composition is composed substantially only of the polyimide precursor means that the content of the resin other than the polyimide precursor contained in the resin composition is 3 mass% or less of the content of the polyimide precursor desirable.

(Polyimide precursor)

The polyimide precursor is preferably a polyimide precursor containing a repeating unit represented by the formula (1).

Equation (1)

(2)

In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group.

A ²¹ and A ²² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.

R ²¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aryl group. Examples of the divalent organic group include a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, An aryl group having 1 to 20 carbon atoms, or a combination thereof, and more preferably a group consisting of an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include the following.

(3)

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

Specifically, R ²¹ may be a diamine residue remaining after removal of the amino group of the diamine shown below.

1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 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 isophorone diamine; 4,4'- and 3,3'-diaminodiphenyl ethers, 4,4'- and 3,3'-diaminobiphenyls, 4,4'- and 3,3'-diaminodiphenyl ethers, 4,4'- 4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2- Bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2- Amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis 4-amino-3-hydroxyphenyl) sulfone, (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3 , 3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-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- Fluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3' Phenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthra Non-3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'- Diphenylsulfone, 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 Bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 2-bis (4-aminophenyl) octafluorobutane, 1, 4-bis (4-aminophenyl) hexafluoropropane, 5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane , 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- Bis [4- (4-aminophenoxy) -3,5-bis (triphenylphosphine) hexafluoropropane, bis [ (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (4-amino- 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- Ropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4' - &lt; / RTI &gt; diamino-2,2'-bis At least one diamine selected from the group consisting of 2,2 ', 5,5', 6,6'-hexafluorotolidine and 4,4'-diamino-quaterphenyl.

The diamine residue remaining after removal of the amino group of the diamines (DA-1) to (DA-18) shown below may also be mentioned as an example of R ²¹ .

[Chemical Formula 4]

[Chemical Formula 5]

The diamine residue remaining after removal of the amino group of the diamine having two or more alkylene glycol units in the main chain may also be mentioned as an example of R &lt; ²¹ &gt;. It is preferably a diamine residue containing two or more of ethylene glycol chain and propylene glycol chain in total of one molecule, more preferably a diamine residue not containing an aromatic ring. D-400, D-2000, and D-4000 (all trade names, trade names, and registered trade names) Propane-2-amine, 1- (1- (1- (2-aminopropoxy) ethoxy) ) Propan-2-yl) oxy) propane-2-amine, but are not limited thereto. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148 and EDR-176 are shown below.

[Chemical Formula 6]

In the above, x, y and z are average values.

In the formula (1), R ²² represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, more preferably a group represented by the following formula (1-1) or (1-2).

(1-1)

(7)

In the formula (1-1), R ¹¹² represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a single bond or a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and -NHCO - and combinations thereof, and is preferably selected from the group consisting of a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- and -SO ₂ - it is more preferably a divalent _{group, -CH 2 -, -C (CF} 3) 2 -, -C (CH 3) 2 -, -O-, -CO-, -S- and -SO ₂ - consisting of Lt; 2 &gt; is more preferable.

Equation (1-2)

[Chemical Formula 8]

R ²² is a tetracarboxylic acid residue remaining after removing an acid anhydride group from a tetracarboxylic acid dianhydride. Specifically, tetracarboxylic acid residues remaining after removing the acid anhydride group from the following tetracarboxylic acid dianhydride and the like can be mentioned.

(PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic acid dianhydride, 3,3 ' 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic acid dianhydride, 2 , 2 ', 3,3'-diphenylmethane tetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride Water, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4 (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride , 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4, 5,6-naphthalenetetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5- Naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane (3,4-dicarboxyphenyl) ethane dianhydride and 1,2,3,4-benzenetetracarboxylic acid dianhydride, an alkyl derivative having 1 to 6 carbon atoms and an alkyl derivative having 1 to 6 carbon atoms, At least one tetracarboxylic acid dianhydride selected from the group consisting of alkoxy derivatives of the formula

The remaining tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) shown below may also be mentioned as an example of R ²² .

[Chemical Formula 9]

From the viewpoint of solubility in an alkali developing solution, it is preferable that R ²² has an OH group. More specifically, as R ²² , a tetracarboxylic acid residue remaining after removing the acid anhydride group from (DAA-1) to (DAA-5) may be mentioned.

In the formula (1), R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group represented by R ²³ and R ²⁴ include a linear or branched alkyl group, a cyclic alkyl group, a group containing an aromatic group, and a radical polymerizable group. In the present invention, at least one of R ²³ and R ²⁴ is preferably a group containing a radically polymerizable group. According to this aspect, the effect of the present invention tends to be obtained more remarkably. The photosensitive resin composition containing the polyimide precursor can be preferably used as a negative photosensitive resin composition. Examples of the radical polymerizable group include groups having an ethylenic unsaturated bond. Specific examples of the radical polymerizable group include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

[Chemical formula 10]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and more preferably a methyl group.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ - or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of suitable R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butenediyl group, a 1,3-butenediyl group, a pentamethylene group, a hexamethylene group, _{dodeca-methylene, -CH 2 CH (OH) CH} 2 - it may be mentioned, ethylene group, propylene group, trimethylene _{group, -CH 2 CH (OH) CH} 2 - is more preferable. Particularly preferred are combinations wherein R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

The number of carbon atoms of the linear or branched alkyl group is preferably from 1 to 30. Specific examples include 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, a dodecyl group, a tetradecyl group, an octadecyl group, butyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.

The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, a vinyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, . Among them, a cyclohexyl group is preferable from the viewpoint of compatibility with high sensitivity.

Examples of the aromatic group include a substituted or unsubstituted benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, an azulene ring group, a heptareylene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group, A pyridine ring, a pyrrole ring, a furan ring, a thiophen ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrazine ring, , Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophen ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring , A quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chroman ring, a xanthine ring, a phenoxathiene ring, Ventilation or Rajin can be ventilated. Benzene ventilation is preferred.

When A ²² is an oxygen atom and R ²³ is a hydrogen atom, and / or when A ²¹ is an oxygen atom and R ²⁴ is a hydrogen atom, the polyimide precursor may be a tertiary An amine compound and an opposite salt may be formed. An example of such a tertiary amine compound having an ethylenic unsaturated bond is N, N-dimethylaminopropyl methacrylate.

In the case of alkali development, it is preferable that the polyimide precursor has a fluorine atom in the structural unit in order to improve the resolution. The fluorine atom imparts water repellency to the surface of the film during the alkali development, so that intrusion from the surface or the like can be suppressed. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less from the viewpoint of solubility in an aqueous alkali solution.

For the purpose of improving adhesion with the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane and the like can be given as a diamine component.

In order to improve the storage stability of the resin composition, the main chain end of the polyimide precursor is encapsulated with a terminal sealing agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound Sealing). Of these, monoamine is more preferably used. Preferred examples of the monoamine include aniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy- Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1 -hydroxy- Carboxy-7-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, Aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, , 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3- No phenol, there may be mentioned 4-aminophenol, 2-amino-thio phenol, 3-amino-thio phenol, 4-amino-thio phenol and the like. Two or more of them may be used, or a plurality of other end groups may be introduced by reacting a plurality of terminal end-capping agents.

The polyimide precursor may be composed of a repeating unit represented by the formula (1) and another repeating unit which is another polyimide precursor.

When other repeating units are contained, the proportion of other repeating units in the polyimide precursor is preferably 1 to 60 mol%, more preferably 5 to 50 mol%.

The polyimide precursor in the present invention may be configured so as not to substantially contain another polyimide precursor other than the polyimide precursor containing the repeating unit represented by the formula (1). The term substantially not containing means that the content of the other polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 20,000 to 28,000, more preferably 22,000 to 27,000, and still more preferably 23,000 to 25,000. The dispersion degree (Mw / Mn) of the polyimide precursor is not particularly limited, but is preferably 1.0 or more, more preferably 2.5 or more, and more preferably 2.8 or more. The upper limit value of the degree of dispersion of the polyimide precursor is not particularly limited, but is preferably 4.5 or less, and may be 3.4 or less, for example.

(Polyimide)

The polyimide used in the present invention may be any polymer compound having an imide ring and is not particularly limited, but is preferably a compound represented by the following formula (4), a compound represented by the following formula (4) Compound is more preferable. Examples of the radical polymerizable group include the polymerizable groups described above for the polyimide precursor, and preferred ranges are also the same.

Equation (4)

(11)

In the formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

In the case where the polyimide has a radically polymerizable group, a radical polymerizable group may be introduced into at least one of R ¹³¹ and R ¹³² , and as shown in the following formula (4-1) or (4-2) A radical polymerizable group may be introduced.

Equation (4-1)

[Chemical Formula 12]

In the formula, R ¹³³ is a radical polymerizable group, and the other groups are synonymous with the formula (4).

Equation (4-2)

[Chemical Formula 13]

In the formula, at least one of R ¹³⁴ and R ¹³⁵ is a radical polymerizable group, the other is an organic group, and the other group agrees with the formula (4).

As the divalent organic group represented by R ¹³¹ , the same groups as those of R ²¹ in the formula (1) of the above-mentioned polyimide precursor are exemplified, and the preferable range is also the same. As the tetravalent organic group represented by R ¹³² , the same groups as those of R ²² in the formula (1) of the aforementioned polyimide precursor are exemplified, and the preferable range is also the same.

The polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more. When the imidization ratio is 85% or more, film shrinkage due to cyclization occurring when imidization by heating is reduced, and occurrence of warpage can be suppressed.

The polyimide may contain a repeating unit containing two or more different kinds of R ¹³¹ or R ¹³² in addition to the repeating structural unit of the above formula (4) based on R ¹³¹ or R ¹³² , all of which are monomers. In addition to the repeating units of the above formula (4), the polyimide may also contain other types of repeating structural units.

The polyimide can be obtained by, for example, a method of reacting a tetracarboxylic acid dianhydride and a diamine compound (part of which is substituted with a terminal sealant which is a monoamine) at a low temperature, a method of reacting a tetracarboxylic acid dianhydride (partly an acid anhydride or a monoacid chloride compound Or a mono-active ester compound), a method of reacting a diamine compound with a tetracarboxylic acid dianhydride and an alcohol, followed by reaction with a diamine (partly substituted with a monoamine end-capping agent) and condensation A method in which a diastereomer is obtained by a tetracarboxylic acid dianhydride and an alcohol and then the remaining dicarboxylic acid is acid chloridized and reacted with diamine (part of which is substituted with a terminal sealant such as a monoamine) , A polyimide precursor was obtained, A method in which the imidization reaction is stopped and the imide structure is partially introduced, or a method in which a completely imidized polymer is blended with the polyimide precursor , And a method of partially introducing an imide structure can be used.

Examples of commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by Fuji Film) and Matrimide 5218 (manufactured by HUNTSMAN).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. When two or more polyimides are contained, it is preferable that the weight average molecular weight of at least one polyimide is in the above range.

(Polybenzoxazole precursor)

In the present invention, the polybenzoxazole precursor is not particularly limited as to the structure and the like, but is preferably a compound containing a repeating unit represented by the following formula (3).

Equation (3)

[Chemical Formula 14]

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

In the formula (3), R ¹²³ and R ¹²⁴ are each the same as R ²³ in the formula (1), and their preferable ranges are also the same.

In the formula (3), the divalent organic group represented by R ¹²¹ is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable.

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight chain or branched (preferably straight chain) aliphatic group is preferable, and a dicarboxylic acid composed of a straight chain or branched (preferably straight chain) aliphatic group and two COOH is more preferable Do. The number of carbon atoms in the straight chain or branched (preferably straight chain) aliphatic group is preferably from 2 to 30, more preferably from 2 to 25, still more preferably from 3 to 20, particularly preferably from 4 to 15 , And even more preferably from 5 to 10. The straight-chain aliphatic group is preferably an alkylene group. Specific examples of the dicarboxylic acid having a straight chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-methylglutaric acid, 2-methylglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberous acid, azelaic acid, sebacic acid, hexadecafluorosevac acid, 1,9-nonanedic acid, dodecanedioic acid, tri Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexoic acid diacid, docosaic acid, hexadecanedioic acid, Butyric acid diacid, octacosic diacid, nonanoic acid diacid, triacontanic acid, hexanedic acid diacid, ditolacontanic acid, diglycolic acid , And dicarboxylic acids represented by the following formulas.

[Chemical Formula 15]

(Wherein Z is a hydrocarbon group having 1 to 6 carbon atoms and n is an integer of 1 to 6)

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

[Chemical Formula 16]

Wherein, A is -CH ₂ - a _{-, -O-, -S-, -SO 2} -, -CO-, -NHCO-, -C (CF 3) 2 -, and -C (CH _{3) 2} Or a divalent group selected from the group consisting of

As specific examples of the dicarboxylic acid containing an aromatic group, 4,4'-carbonylbenzoic acid and 4,4'-dicarboxy diphenylether terephthalic acid are preferable.

In the formula (3), R ¹²² represents a tetravalent organic group. As the tetravalent organic group, the groups described in R ²² in the above formula (1) are exemplified, and the preferable range is also the same.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and even more preferably 9200 to 11200. The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited, but is preferably 2.6 or less, more preferably 2.5 or less, more preferably 2.4 or less, still more preferably 2.3 or less, and 2.2 or less Is more preferable.

(Polybenzoxazole)

The polybenzoxazole may be any compound having a benzoxazole ring, and is not particularly limited, but is preferably a compound having a repeating unit represented by the following formula (X), and is a compound represented by the following formula (X) Is more preferable. As the radically polymerizable group, the radically polymerizable group described above for the polyimide precursor can be exemplified, and the preferable range is also the same.

[Chemical Formula 17]

In the formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

In the case where the polybenzoxazole has a radical polymerizable group, a radical polymerizable group may be introduced into at least one of R ¹³³ and R ¹³⁴ , and as shown in the following formula (X-1) or (X-2) A radically polymerizable group may be introduced at the end of the oxazole.

The formula (X-1)

[Chemical Formula 18]

In the formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a radically polymerizable group, the other is an organic group, and the other group agrees with the formula (X).

The formula (X-2)

[Chemical Formula 19]

In the formula (X-2), R ¹³⁷ is a radical polymerizable group, the others are substituents, and the other groups are synonymous with the formula (X).

As the divalent organic group represented by R ¹³³ , an aliphatic or aromatic group can be exemplified. Specific examples include the groups described for R ¹²¹ in the formula (3) of the polybenzoxazole precursor, and the preferable range is also the same.

As the tetravalent organic group represented by R ¹³⁴ , the groups described in R ¹²² in the formula (3) of the polybenzoxazole precursor are exemplified, and the preferable range is also the same.

Polybenzoxazole is, the formula (X), which all include one type R ¹³³ or R ¹³⁴ above formula (X) repeats R ¹³³ or R ^134, a different kind of two or more in addition to the structural unit represented by based on May also be included. In addition to the repeating unit of the above formula (X), the polybenzoxazole may also include other types of repeating structural units.

The polybenzoxazole can be prepared by, for example, reacting a bisaminophenol derivative with a compound selected from a dicarboxylic acid including R ¹³³ and a dicarboxylic acid dichloride and a dicarboxylic acid derivative of the dicarboxylic acid to form a polybenzoxazole precursor And oxazotizing it using a known oxazolization reaction method. In the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative in which 1-hydroxy-1,2,3-benzotriazole or the like has been previously reacted may be used in order to increase the reaction yield and the like.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.

<< Radical Polymerizable Compound >>

The resin composition of the present invention may further contain a radical polymerizable compound. By containing a radical polymerizable compound, it can be suitably used as a negative-working photosensitive resin composition. Further, a cured film excellent in heat resistance can be formed. As the radical polymerizing compound, a compound having an ethylenic unsaturated bond is preferable, and a compound containing two or more groups having an ethylenic unsaturated bond is more preferable. The radical polymerizing compound may be, for example, a monomer, a prepolymer, an oligomer and a mixture thereof, and a chemical form such as a multimer thereof. As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable. The radical polymerizing compound in the present invention is a component different from the above-mentioned resin. That is, a polyimide precursor having a radically polymerizable group, a polyimide having a radically polymerizable group, a polybenzoxazole precursor having a radically polymerizable group, and a polybenzoxazole having a radically polymerizable group correspond to a resin.

In the present invention, a monomer-type radical polymerizing compound (hereinafter also referred to as a radical polymerizing monomer) is a compound different from a polymer compound. The radical polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound having a molecular weight of 900 or less. The molecular weight of the radically polymerizable monomer is usually 100 or more.

It is also preferred that the oligomeric type of radically polymerizable compound is typically a relatively low molecular weight polymer and is a polymer having from 10 to 100 radically polymerizable monomers combined. As the molecular weight, the weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is preferably 2000 to 20,000, more preferably 2,000 to 15,000, and still more preferably 2,000 to 10,000.

The functional group number of the radical polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule. From the viewpoint of resolution, the resin composition preferably contains at least one radically polymerizable compound having two or more radically polymerizable groups and at least one radically polymerizable compound having two to four functional groups Is more preferable.

Examples of the radical polymerizable compound include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), esters thereof and amides, An ester of a carboxylic acid and a polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and a polyvalent amine compound. Further, 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 mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, or a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, a compound group substituted by an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, or the like may be used in place of the above unsaturated carboxylic acid. As a specific example, reference can be made to the description of paragraphs 0113 to 0122 of Japanese Laid-Open Patent Publication No. 2016-027357, the contents of which are incorporated herein by reference.

As the radical polymerizing compound, a compound having a boiling point of 100 캜 or more at normal pressure is also preferable. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (Meth) acrylate, tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as ethylene glycol, propylene ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, Japanese Patent Application Laid-Open No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Laid-Open Patent Publication No. 51-037193, (Meth) acrylates described in JP-A-48-064183, JP-A-49-043191, JP-A-52-030490, polyester acrylates, epoxy resins And epoxy acrylates which are reaction products of (meth) acrylic acid and the like, and mixtures thereof. Also, the compounds described in paragraphs 0254 to 0257 of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

Examples of the radical polymerizable compound include compounds having a fluorene ring and having an ethylenically unsaturated bond, as described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, Can also be used. As other examples, specific unsaturated compounds described in JP-A-46-043946, JP-A-1-040337 and JP-A-1-040336, and JP-A- Vinyl phosphonic acid-based compounds described in &quot; 025493 &quot; A compound containing a perfluoroalkyl group described in JP-A-61-022048 may also be used. Also, Japan Adhesion Society vol. 20, No. 7, pages 300 to 308 (1984), which are incorporated herein by reference, as photopolymerizable monomers and oligomers.

In addition to the above, compounds represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical Formula 20]

[Chemical Formula 21]

In the above formulas, n is an integer of 0 to 14, and m is an integer of 0 to 8. The plurality of R and T present in the molecule may be the same or different.

At least one of the plurality of R's in each of the compounds represented by the above formulas (MO-1) to (MO-5) is -OC (═O) CH═CH ₂ or -OC (═O) ₃ ) = CH ₂ .

Specific examples of the compounds represented by the above formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779.

Japanese Unexamined Patent Publication (Kokai) No. 10-62986 discloses a process for producing (meth) acrylate by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described together with specific examples of the formulas (1) and (2) The compound may also be used as a radical polymerizing compound. The compounds described in paragraphs 0104 to 0131 of Japanese Laid-Open Patent Publication No. 2015-187211 may also be used as radical polymerizing compounds, and these contents are incorporated herein by reference.

Examples of the radical polymerizable compound include dipentaerythritol triacrylate (KAYARAD D-330 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 manufactured by Nippon Kayaku (Trade name: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (trade name: A-TMMT, manufactured by Shin Nakamura Kagaku Kogyo K.K.), dipentaerythritol penta (Meth) acryloyl groups of ethylene glycol and propylene glycol moieties are intervened between the acrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Kagaku Kogyo Co., The structure is preferable. These oligomer types can also be used. Preferred examples thereof include pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2). SR209 manufactured by Satomar Co., Ltd. may also be used.

The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Commercially available products include, for example, M-510 and M-520 which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd. The preferred acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. When the acid value of the compound is in the above range, the preparation and handling properties are excellent, and further, the developing property is excellent. Radical polymerization property is also good.

As the radical polymerizing compound, a compound having a caprolactone structure may be used. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as pentaerythritol, pentaerythritol, dipentaerythritol, trilpentaerythritol, glycerin, diglycerol, and trimethylol melamine with? -Caprolactone (Meth) acrylate. Among them, a compound represented by the following formula (C) is preferable.

In formula (C)

[Chemical Formula 22]

Wherein all six Rs are groups represented by the following formula (D), or one to five of the six Rs are groups represented by the following formula (D), and the remainder is a group represented by the following formula (E).

In formula (D)

(23)

In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bonding bond.

(E)

&Lt; EMI ID =

In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

Such a compound having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (in the formulas (C) to (E) D) number = 2, R ¹ are both a hydrogen atom in the group represented by), DPCA-30 (the same formula, the number = 3, R ¹ of a group represented by m = 1, formula (D) are all hydrogen atoms Compound (DPCA-60) (the same formula, m = 1, the number of groups represented by formula (D) = 6 and R ¹ are all hydrogen atoms), DPCA-120 D) = 6, and R &lt; ¹ &gt; are all hydrogen atoms.

The radical polymerizing compound is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

(25)

In the formulas (i) and (ii), E independently represents - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) y each independently represents an integer of 0 to 10, and X represents, independently of each other, a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.

The total number of (meth) acryloyl groups in the formula (i) is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In formula (ii), the sum of the (meth) acryloyl groups is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60. Provided that when the sum of each n is 0, any one of X is a carboxyl group.

In the formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

The - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the formula (i) or the formula Shape is preferable. Particularly, in the formula (ii), it is preferable that all of the six X's are acryloyl groups.

Examples of commercially available products of the compounds represented by the formulas (i) and (ii) include SR-494 which is tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., Ltd., pentyleneoxy (trade name) manufactured by Nippon Kayaku Kabushiki Kaisha DPCA-60, which is a hexafunctional acrylate having 6 chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the radical polymerizing compound include compounds described in JP-A-48-041708, JP-A-51-037193, JP-A-2-032293, JP-A-2-016765 There are ethylene acrylic acid esters, ethylene acrylic acid esters, ethylene acrylic acid esters, ethylene acrylate esters, ethylene oxide esters, A yutein compound having a skeleton is also suitable. Further, addition polymerizable monomers having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 It can also be used.

NK Ester M-9300, NK Ester A-9300, UA-7200 (produced by Sanyo Kokusaku Pulp Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M- UA-306I, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Kagaku Kogyo Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and Blemmer PME400 (manufactured by Nichiyu K.K.).

The radical polymerizing compound preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the equation is a connecting hand.

(26)

Specific examples of the compound having a partial structure include, for example, trimethylol propane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide denatured tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylol propane tetra Pentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and the like.

In the resin composition, the content of the radical polymerizable compound is preferably 1 to 50 mass% with respect to the total solid content of the resin composition from the viewpoint of good radical polymerization and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30 mass% or less.

The mass ratio of the resin (preferably a polyimide precursor) to the radical polymerizable compound (resin / radical polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70 More preferably 90/10 to 50/50. When the mass ratio of the resin to the radical polymerizing compound is within the above range, a cured film having better curing properties and heat resistance can be formed. The radical polymerizing compound may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total amount falls within the above range.

<< Photopolymerization initiator >>

The resin composition of the present invention includes a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferred. When the resin composition of the present invention contains a photo-radical polymerization initiator, the resin composition is applied to a substrate such as a semiconductor wafer to form a resin composition layer, and then light is irradiated to cause curing due to radicals, It is possible to lower the solubility in the solution. Thereby, there is an advantage that, for example, a resin composition layer is exposed through a photomask having a pattern for masking only the electrode portion, whereby a region having different solubility can be easily produced in accordance with a pattern of an electrode or the like.

The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light in the visible region from the ultraviolet region is preferable. It may also be an activator that generates an action with a photo-excited sensitizer and generates active radicals. The photopolymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured by a known method. For example, it is preferable to use an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) with an ethyl acetate solvent at a concentration of 0.01 g / L.

As the photopolymerization initiator, known compounds can be arbitrarily used. Examples of the compound include a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, a compound having a trihalomethyl group, etc.), an acylphosphine compound such as acylphosphine oxide , Oxa compounds such as hexaaryl biimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds , Metallocene compounds, organic boron compounds, iron arene complexes and the like. For details of these, reference may be made to the description of paragraphs 0165 to 0182 of Japanese Laid-Open Patent Publication No. 2016-027357, the contents of which are incorporated herein by reference. As the ketone compound, for example, the compound described in paragraph 0087 of Japanese Laid-Open Patent Publication No. 2015-087611 is exemplified, and the content is hereby incorporated by reference. In commercial products, Kayakyure-DETX (manufactured by Nippon Kayaku Co., Ltd.) is suitably used.

As the photopolymerization initiator, an? -Hydroxy ketone compound, an? -Amino ketone compound, an acylphosphine compound and a metallocene compound can also be suitably used. More specifically, for example, the photopolymerization initiator disclosed in JP-A-10-291969 and the photopolymerization initiator disclosed in JP-A-4225898 can be used.

As the? -hydroxyketone compound, IRGACURE-184 (registered trademark of IRGACURE), DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (trade name;

As the? -amino ketone compound, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the? -amino ketone compound, compounds described in JP-A-2009-191179 in which the maximum absorption wavelength is matched with a wavelength light source such as 365 nm or 405 nm can be used.

As the acylphosphine compound, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like can be given. Commercially available IRGACURE-819 or IRGACURE-TPO (all trade names, manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using an oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a thermal base generator.

Specific examples of the oxime compounds include the compounds described in JP 2001-233842 A, the compounds described in JP-A 2000-080068, and JP-A 2006-342166. Preferred oxime compounds include, for example, 3-benzoxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

(Commercially available from BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Co., Ltd., JP-A-2012-014052), IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 03, IRGACURE OXE 03 2) are also suitably used. ADEKA ACKNES NCI-831 and ADEKA ACKLS NCI-930 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) Can also be used. In addition, DFI-091 (manufactured by Daito Kikusui Co., Ltd.) can be used. It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Publication No. 2014-500852, paragraph 0345, Japanese Laid- The compound (C-3) described in paragraph 0101 of Japanese Patent Application Laid-Open No. 164471 and the like.

Examples of the most preferred oxime compounds include oxime compounds having a specific substituent group as disclosed in Japanese Unexamined Patent Application Publication No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

As the photopolymerization initiator, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole And a 3-aryl substituted coumarin compound, and at least one kind selected from a trihalomethyltriazine compound, an? -Hydroxy ketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metal An oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, and an acetophenone compound And at least one kind selected from a trihalomethyltriazine compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound More preferred are metallocene compounds or oxime compounds, and oxime compounds are particularly preferred.

The photopolymerization initiator may be at least one selected from the group consisting of N, N'-tetraalkyl-4,4'-diaminobenzophenone (N, N'-tetramethylphenol) such as benzophenone and N, Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1, Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl dimethyl ketal compounds such as benzyl dimethyl ketal, And the like can also be used. In addition, a compound represented by the following formula (I) may be used.

(27)

In the formula (I), R ⁵⁰ represents an alkyl group having 1 to 20 carbon atoms; An alkyl group having 2 to 20 carbon atoms which is interrupted by at least one oxygen atom; An alkoxy group having 1 to 12 carbon atoms; A phenyl group; An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms And a phenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms; Or biphenyl; R ⁵¹ is a group represented by the formula (II) or a group identical to R ⁵⁰ ; R ⁵² to R ⁵⁴ each independently represent alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, Rosen.

(28)

In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

The photopolymerization initiator may be a compound described in paragraphs 0048 to 0055 of WO2015 / 125469.

The content of the photopolymerization initiator is preferably from 0.1 to 30 mass%, more preferably from 0.1 to 20 mass%, and still more preferably from 0.1 to 10 mass%, based on the total solid content of the resin composition. The photopolymerization initiator may contain only one kind or two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.

<< Polymerization inhibitor >>

The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert- butylcatechol, p-benzoquinone, Benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis - phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylene diamine diacetic acid, 1,2-cyclohexanediamine diacetic acid, glycol ether 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis 5-tert-butyl) phenylmethane and the like are suitably used. It is also possible to use the polymerization inhibitor described in paragraph 0060 of Japanese Laid-Open Patent Publication No. 2015-127817 and the compound described in paragraphs 0031 to 0046 of WO2015 / 125469.

When the resin composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the resin composition. The polymerization inhibitor may be one kind alone, or two or more kinds. When two or more types of polymerization inhibitor are used, the total amount is preferably in the above range.

<< Photobase generator >>

The resin composition of the present invention may contain a photobase generator. The photobase generator is a substance which generates a base by exposure and does not exhibit activity under normal conditions of normal temperature and pressure. However, if irradiation and heating of an electromagnetic wave are performed as an external stimulus, a base (basic substance) It is not. The base generated by the exposure serves as a catalyst for curing the polyimide precursor by heating, and thus can be suitably used in the negative photosensitive resin composition.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern and can be a general content. The content of the photobase generator is preferably in a range of 0.01 part by mass or more and less than 30 parts by mass, more preferably in a range of 0.05 part by mass to 25 parts by mass, more preferably 0.1 part by mass to 20 parts by mass, More preferably within the range of the mass part.

In the present invention, known compounds can be used as photo-base generators. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Tsunooka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. As described in Technol., 19, 81 (2006), it is also possible to use a transition metal compound complex or a compound having a structure such as an ammonium salt, or a compound in which a base component is a salt Ionic compound in which the base component is neutralized by a urethane bond or a oxime bond such as a neutralized ionic compound, a carbamate derivative, an oxime ester derivative or an acyl compound. It is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The basic substance generated from the photo-base generator is not particularly limited, but a compound having an amino group, particularly, a polyamine such as a monoamine or a diamine, and an amidine can be given.

The generated basic substance is preferably a compound having an amino group having a higher basicity. And the dehydration condensation reaction in the imidization of the polyimide precursor is strong, so that the catalytic effect in dehydration condensation reaction at a lower temperature can be manifested by addition of a smaller amount. Eventually, since the catalytic effect of the generated basic substance is large, the apparent sensitivity as the resin composition is improved. From the viewpoint of the catalytic effect, amidine and aliphatic amine are preferable.

The photobase generator is preferably a photobase generator that does not contain a salt in its structure. It is preferable that there is no charge on the nitrogen atom of the base portion generated in the photobase generator. It is preferable that the base of the photobase generator is latent using a covalent bond and the generation mechanism of the base is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved, Is more preferable. If the photo-base generator does not contain a salt in its structure, the photo-base generator can be made neutral, so that the solvent solubility is good and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

Further, for the same reason as described above, it is preferable that the base generated as described above is latent by using a covalent bond. It is more preferable that the generated base is latent using an amide bond, a carbamate bond, or an oxime bond.

As photobase generators, photobase generators having a cinnamic acid amide structure described in JP-A-2009-080452 and WO2009 / 123122, JP-A-2006-189591 and JP- A photobase generator having a carbamate structure described in JP-A-247747, a photobase generator having a oxime structure or a carbamoyl oxime structure described in JP-A-2007-249013 and JP-A-2008-003581 .

Other examples of the photoacid generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP-A No. 2012-093746, compounds described in paragraphs 0022 to 0069 of JP-A No. 2013-194205, The compounds described in paragraphs 003 to 0044 of Patent Publication No. 2013-204019 and the compounds described in paragraph No. 0052 of WO2010 / 064631 can be mentioned.

<< Thermal Base Generator >>

The resin composition of the present invention may contain a thermal base generator. Examples of the thermal base generator include a thermal base generating agent containing at least one selected from an acidic compound (A1) generating a base upon heating at 40 ° C or higher and an ammonium salt (A2) having an anion and an ammonium cation having a pKa1 of 0 to 4 I am preferable. Here, pKa1 indicates an algebraic sign (-Log ₁₀ Ka) of the dissociation constant Ka of the first proton of the polyvalent acid.

The acidic compound (A1) and the ammonium salt (A2) generate a base upon heating, so that the cyclization reaction of the polyimide precursor or the like can be promoted by the base generated from these compounds, . In addition, even when these compounds coexist with a polyimide precursor or the like which is cyclized and cured by a base, the cyclization of the polyimide precursor or the like hardly progresses unless heated, so that a resin composition excellent in storage stability can be prepared.

In the present specification, the acidic compound used in the present specification means that 1 g of the compound is taken out of the container, 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1/4) is added, Means a compound having a pH value measured at 20 캜 using a pH meter of less than 7 with stirring.

The base-generating temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, more preferably 120-200 ° C. The upper limit of the nucleation temperature is preferably 190 占 폚 or lower, more preferably 180 占 폚 or lower, and still more preferably 165 占 폚 or lower. The lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher.

When the base-generating temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 占 폚 or higher, a base is hardly generated during storage, so that a resin composition excellent in stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is not higher than 200 占 폚, the cyclization temperature of the polyimide precursor can be lowered. The base generation temperature can be measured, for example, by differential scanning calorimetry, by heating the compound up to 250 ° C at 5 ° C / min in pressure-resistant capsules, reading the peak temperature of the lowest exothermic peak, The peak temperature can be measured as the nucleation temperature.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. The tertiary amine has a high basicity, so that the cyclization temperature of the polyimide precursor can be lowered. The boiling point of the base generated by the thermal base generator is preferably 80 占 폚 or higher, more preferably 100 占 폚 or higher, and most preferably 140 占 폚 or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. The molecular weight is a theoretical value obtained from the structural formula.

The acidic compound (A1) preferably contains at least one selected from an ammonium salt and a compound represented by the formula (A1) described below.

The ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound which generates a base upon heating at 40 ° C or higher (preferably 120-200 ° C), and may be a compound containing an acidic compound capable of generating a base at a temperature of 40 ° C or higher A compound other than an acidic compound which generates a base upon heating may be used.

In the present invention, the ammonium salt means ammonium cations represented by the following formula (101) or (102) and salts with anions. The anion may be bonded to any part of the ammonium cations through a covalent bond or may be outside the molecule of the ammonium cation, preferably outside the molecule of the ammonium cation. Further, the presence of the anion outside the molecule of the ammonium cation means the case where the ammonium cation and the anion are not bonded through a covalent bond. Hereinafter, an anion outside the molecule of the cation portion is also referred to as a counter anion.

[Chemical Formula 29]

In the formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and the formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may combine with each other to form a ring.

In the present invention, the ammonium salt preferably has an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and further preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polyimide precursor or the like can be cyclized to a low temperature and, further, the stability of the resin composition can be improved. When the pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the resin composition is good. When the pKa1 is 0 or more, the generated base is hardly neutralized and the cyclization efficiency of the polyimide precursor and the like is good.

As the kind of anion, one type selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion is preferable, and a carboxylic acid anion is more preferable because the salt stability and the thermal decomposition ability can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this embodiment, it is possible to provide a thermal base generating agent capable of further improving the stability, curability and developability of the resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability and developability of the resin composition can be further improved.

In the present invention, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and more preferably 3.2 or less. According to this embodiment, the stability of the resin composition can be further improved.

Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and is determined by Determination of Organic Structures by Physical Methods (by Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; , Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Dawson, RMC et al; Oxford, Clarendon Press, 1959). For the compound not described in these documents, the value calculated from the structural formula using the software of ACD / pKa (ACD / Labs) is used.

In the present invention, the carboxylic acid anion is preferably represented by the following formula (X1).

(30)

In the formula (X1), EWG represents an electron-attracting group.

In the present invention, the electron attractive group means that the substituent constant σm of Hammett shows a positive value. Here, σm is explained in detail by TSUNO YOHO, Journal of the Organic Chemistry of Japan, Vol. 23, No. 8 (1965), pp. 631-642. The electron donating group of the present invention is not limited to the substituents described in the above documents.

Examples of the substituent whose σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), CH ₂ ═CH group = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group . Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

(31)

In the formulas, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aryl group.

In the present invention, the carboxylic acid anion is also preferably represented by the following formula (X).

(32)

In formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, -NR ^X - and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group , An alkenyl group or an aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenylimino acetic acid anion and oxalic acid anion. These can be preferably used.

It is preferable that the ammonium cation is represented by any one of the following general formulas (Y1-1) to (Y1-6).

(33)

In the above general formula, R ¹⁰¹ represents an n-valent organic group,

R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group,

R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group,

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring,

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,

n represents an integer of 1 or more,

m represents an integer of 0 to 5;

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or polycyclic. Examples of the linking group in the case where the above groups are bonded to form a ring include divalent linking groups selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a divalent aryl group, and combinations thereof have. Specific examples of the ring formed include a pyrrole ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, An isoindole ring, a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a cinnoline ring, a carbazole ring, and the like.

In the present invention, the ammonium cations, will appear by the formula (Y1-1) or a group represented by the formula (Y1-2) is preferably represented by the structure, and formula (Y1-1) or a group represented by the formula (Y1-2), R ¹⁰¹ is an aryl group , More preferably a structure represented by formula (Y1-1), and R &lt; ¹⁰¹ &gt; is an aryl group is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y).

(34)

In formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, n Represents an integer of 1 or more.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, but an alkyl group, an alkenyl group or an aryl group is preferable.

R ¹¹ and R ¹² are preferably a hydrogen atom.

R ¹³ to R ¹⁵ represent a hydrogen atom or a hydrocarbon group.

Examples of the hydrocarbon group include the hydrocarbon groups described for R ¹¹ and R ¹² described above. R ¹³ to R ¹⁵ are preferably an alkyl group, and preferred embodiments thereof are the same as those described in R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include a cyclic aliphatic (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or polycyclic. As a linking group when R ¹⁴ and R ¹⁵ are bonded to form a ring, a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, . Specific examples of the ring formed include a pyrrole ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, An isoindole ring, a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a cinnoline ring, a carbazole ring, and the like.

R ¹³ ~ R ¹⁵ is, R ¹⁴ and R ¹⁵ is either to form a ring by combining to each other, or R ¹³ is, (preferably having a carbon number of 6 to 18 more), with a straight chain alkyl group having 5 ~ 30, R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this embodiment, it is possible to easily generate an amine species having a high boiling point.

The total number of carbon atoms of R ¹³ , R ¹⁴ and R ¹⁵ is preferably 7 to 30, more preferably 10 to 20, from the viewpoints of the basicity or boiling point of the generated amine species.

Further, for the reason that amine species having high boiling points are easily generated, the formula weight of "-NR ¹³ R ¹⁴ R ¹⁵ " in formula (Y) is preferably 80 to 2000, more preferably 100 to 500 .

As an embodiment for further improving the adhesion with a metal layer such as copper, it is preferable that R ¹³ and R ¹⁴ in the formula (Y) are a methyl group or an ethyl group and R ¹⁵ is a linear, branched or cyclic alkyl group having 5 or more carbon atoms , And an aryl group. R ¹³ and R ¹⁴ are methyl groups and R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, a cyclic alkyl group having 6 to 10 carbon atoms or a phenyl group, and R ¹³ and R ¹⁴ are methyl groups , R ¹⁵ is a straight-chain alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, a cyclic alkyl group having 6 to 8 carbon atoms, or a phenyl group. By lowering the hydrophobicity of the amine species in this manner, the affinity between the metal layer and the polyimide or the like can be increased even when the amine is adhered to the metal layer such as copper.

In the present invention, it is also preferable that the acidic compound is a compound represented by the following formula (A1). This compound is acidic at room temperature, but the carboxyl group is lost by decarbonation or dehydration cyclization due to heating, so that the neutralized and inactivated amine moiety becomes active to become basic. Hereinafter, Formula (A1) will be described.

The formula (A1)

(35)

In formula (A1), A ¹ represents an organic group of p, R ¹ represents a monovalent organic group, L ¹ represents an (m + 1) -valent linking group, m represents an integer of 1 or more, Represents an integer.

In the formula (A1), A ¹ represents an organic group of p. Examples of the organic group include an aliphatic group and an aromatic group, and an aromatic group is preferable. By making A ¹ an aromatic group, it is easy to generate a base having a high boiling point at a lower temperature. By increasing the boiling point of the generated base, volatilization or decomposition due to heating at the time of curing of the polyimide precursor can be suppressed and the cyclization of the polyimide precursor can proceed more effectively.

Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group.

The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl, ethyl, tert-butyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl and adamantyl.

The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, and even more preferably from 2 to 10. The alkenyl group may be linear, branched or cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group.

Examples of the divalent or higher valent aliphatic group include groups obtained by removing one or more hydrogen atoms from the above monovalent aliphatic groups.

The aromatic group may be monocyclic or polycyclic. The aromatic group may be an aromatic heterocyclic group containing a hetero atom. The aromatic group may have a substituent or may be unsubstituted. Non-substitution is preferred. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, an heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, A thiophene ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, A benzothiophene ring, an isobenzofuran ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxaline ring, a quinoxaline ring, a pyrazine ring, an indolizine ring, A phenanthridine ring group, a phenanthroline ring group, a phenanthroline ring group, a thianthrene ring group, a cyanene ring group, a zircon ring ring, a phenoxathiine ring group, a phenothiazine ring group, and Phena retarder And benzene ventilation is most preferred.

The aromatic group may be connected through a plurality of aromatic rings, a single bond or a linking group described below. As the linking group, for example, an alkylene group is preferable. The alkylene group is preferably both straight-chain and branched. Specific examples of groups in which a plurality of aromatic rings are connected through a single bond or a linking group include a biphenyl group, a diphenylmethane group, a diphenylpropene group, a diphenyl isopropenyl group, a triphenylmethane group, a tetraphenylmethane group, etc. have.

Examples of the substituent which the organic group represented by A ¹ may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group and a butoxycarbonyl group; An aryloxycarbonyl group such as a phenoxycarbonyl group and the like; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxyl group; Alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Halogenated alkyl groups such as fluorinated alkyl groups; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group; An aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumene group, a naphthyl group, an anthryl group and a phenanthryl group; A hydroxyl group; A carboxyl group; Form Diary; A sulfo group; Cyano; An alkylaminocarbonyl group; An arylaminocarbonyl group; Sulfonamide group; Silyl group; An amino group; Monoalkylamino groups; A dialkylamino group; An arylamino group; Diarylamino group; A cyoxy group; Or a combination thereof.

L ¹ represents an (m + 1) -valent linking group. The linking group is not particularly limited and is preferably -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group (preferably a linear or branched An alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a straight-chain or branched alkenylene group having a carbon number of 210) have. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group or an alkenylene group, more preferably a straight chain or branched alkylene group, more preferably a straight chain alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.

R ¹ represents a monovalent organic group. Examples of monovalent organic groups include an aliphatic group and an aromatic group. The aliphatic group and the aromatic group may be those described in A ¹ above. The monovalent organic group represented by R ¹ may have a substituent. As the substituent, those described above may be mentioned.

R ¹ is preferably a group having a carboxyl group. That is, R ¹ is preferably a group represented by the following formula.

-L ² - (COOH) _n

L ² represents an (n + 1) linking group, and n represents an integer of 1 or more.

The linking group represented by L ² includes the groups described in the above-mentioned L ¹ , and the preferable range is also the same. An ethylene group or a methylene group is particularly preferable, and a methylene group is most preferable.

n represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of n is the maximum number of substituents that the linking group represented by L ² can take. When n is 1, it is likely to generate a tertiary amine having a high boiling point by heating at 200 DEG C or less. Further, the stability of the resin composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can take. m is 1, it is easy to generate a tertiary amine having a high boiling point by heating at 200 DEG C or less. Further, the stability of the resin composition can be improved.

p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of p is the maximum number of substituents that the organic group represented by A ¹ can take. When p is 1, it is easy to generate a tertiary amine having a high boiling point by heating at 200 DEG C or less.

In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a).

(36)

In formula (1a), A ¹ represents an organic group of p, L ¹ represents a linking group of (m + 1), L ² represents a linking group of (n + 1), m represents an integer of 1 or more, n Represents an integer of 1 or more, and p represents an integer of 1 or more.

A ¹ , L ¹ , L ² , m, n and p in the general formula (1a) are in agreement with the ranges described in the general formula (A1), and preferable ranges are also the same.

In the present invention, it is preferable that the compound represented by the formula (A1) is N-aryliminioacetic acid. N-arylimino acetic acid is a compound wherein A ¹ in general formula (A1) is an aromatic group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1 . N-arylimino acetic acid is liable to generate a tertiary amine having a high boiling point at 120 to 200 占 폚.

Specific examples of the thermal base generator will be described below, but the present invention is not limited thereto. These may be used alone or in combination of two or more. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18) and (A-19) are compounds represented by the formula (A1). Among the compounds shown below, (A-1) to (A-11), (A-18) ) To (A-21), (A-23), and (A-24).

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

As the thermal base generator used in the present invention, the compounds described in paragraphs 0015 to 0055 of Japanese Patent Application No. 2015-034388 are also preferably used, and these contents are incorporated herein by reference.

When a thermal base generator is used, the content of the thermal base generating agent in the resin composition is preferably from 0.1 to 50 mass% based on the total solid content of the resin composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30 mass% or less, and still more preferably 20 mass% or less.

The thermal base generator may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total amount is in the above range.

<< Thermal radical polymerization initiator >>

The resin composition of the present invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or promotes the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be promoted when the cyclization reaction of the polyimide precursor is promoted. In the case where the polyimide precursor contains a radical polymerizable group, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher intrinsic deterioration can be achieved.

Examples of the thermal radical polymerization initiator include aromatic ketones such as aromatic ketones, onium salts, peroxides, thio compounds, hexaaryl bimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, A compound having a bond, and an azo-based compound. Among them, a peroxide or an azo-based compound is more preferable, and a peroxide is particularly preferable.

The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 캜, more preferably 100 to 120 캜.

Specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Laid-Open Publication No. 2008-063554 can be mentioned.

In commercial products, perbutyl Z and percumyl D (manufactured by Nichiyu K.K.) can be suitably used.

When the resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass based on the total solid content of the resin composition % Is particularly preferable. It is preferable that the thermal radical polymerization initiator is contained in an amount of 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, per 100 parts by mass of the polymerizable compound. According to this embodiment, it is easy to form a cured film excellent in heat resistance. The thermal radical polymerization initiator may be either one kind or two or more kinds. When two or more thermal radical polymerization initiators are used, the total amount is preferably in the above range.

<< Anti-rust >>

The resin composition of the present invention preferably contains a rust inhibitor. By including the rust inhibitor in the resin composition, migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer can be effectively suppressed. Examples of the antirusting agent include the antirust agent described in Japanese Patent Laid-Open Publication No. 2013-015701 paragraph 0094, the compound described in paragraphs 0073 to 0076 of Japanese Laid-Open Patent Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Laid-Open Patent Publication No. 2011-059656, Compounds described in paragraphs 0114, 0116 and 0118 of the publication No. 2012-194520, and the like can be used. Specifically, there may be mentioned heterocyclic rings (pyrrole rings, furan rings, thiophen rings, imidazole rings, oxazole rings, thiazole rings, pyrazole rings, isoxazole rings, isothiazole rings, tetrazole rings, pyridine rings, , A compound having a thiourea group and a mercapto group, a compound having a mercapto group, a compound having a thiourea group and a mercapto group, a compound having a thiourea group and a mercapto group, a compound having a thiourea group, a pyrazine ring, a piperidine ring, Dodephenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. Among them, preferred are triazole-based compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole, and 1,2,4-triazole, 1,2,3-benzotriazole, Tetrazole, 5-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole and 5-phenyl-1H-tetrazole are more preferable and 1H-tetrazole is most preferable. Commercially available products include KEMITEC BT-C (1,2,3-benzotriazole), 1HT (manufactured by Toyobo Co., Ltd., 1H-tetrazole), P5T (manufactured by Toyobo Co., , 5-phenyl-1H-tetrazole), and the like.

When the resin composition contains a rust inhibitor, the content of the rust preventive is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the resin. The rust inhibitor may be of only one type, or may be two or more types. When two or more kinds are used, the total is preferably in the above range.

&Lt; Silane coupling agent &gt;

It is preferable that the resin composition of the present invention contains a silane coupling agent in order to improve the adhesiveness with a metal material used for electrodes, wiring, and the like. Examples of silane coupling agents include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063 to 0071 of WO2011 / 080992A1, paragraphs 0060 to 0061 of JP-A-2014-191252 , Compounds described in paragraphs 0045 to 0052 of Japanese Laid-Open Patent Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. WO2014 / 097594. It is also preferable to use two or more other silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Laid-Open Patent Publication No. 2011-128358. Further, as the silane coupling agent, it is also preferable to use 2 - ((3- (triethoxysilyl) propyl) carbamoyl) benzoic acid, triethoxysilylpropylmaleamic acid, the following compounds. In the following formula, Et represents an ethyl group. As a commercially available product, KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane) may be used.

(37)

The amount of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass based on 100 parts by mass of the resin. When the content of the silane coupling agent is 0.1 part by mass or more, adhesion of the obtained film to the metal layer becomes good, and when the content of the silane coupling agent is 30 parts by mass or less, the heat resistance and mechanical properties of the obtained film become good. The silane coupling agent may be only one kind, or two or more kinds. When two or more kinds are used, the total is preferably in the above range.

<< Solvent >>

In the present invention, when the resin composition is formed into a layer shape by coating, it is preferable to add a solvent to the resin composition. As the solvent, a known solvent can be arbitrarily used. Examples thereof include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and the like.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ? -caprolactone,? -valerolactone, alkyloxyacetate alkyl (for example, alkyloxyacetate, alkyloxyacetate, alkyloxyacetate (for example, methyl methoxyacetate, (For example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, ethyl 3-alkyloxypropionate, ethyl 3-hydroxypropionate, etc.) For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-alkyloxypropionic acid Alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-alkyloxypropionate, Ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, 2-methoxypropionic acid ethyl ester, Methyl propionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, Ethyl, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.

As the aromatic hydrocarbon, for example, toluene, xylene, anisole, limonene and the like are suitably used.

And dimethyl sulfoxide as the sulfoxide side-chain.

The solvent is preferably a mixture of two or more kinds from the viewpoint of improving the surface properties of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, , Cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate A mixed solution composed of two or more kinds is preferable. The combination of dimethyl sulfoxide and? -Butyrolactone is particularly preferable.

When the resin composition has a solvent, the content of the solvent is preferably such that the total solid content concentration of the resin composition is 5 to 80 mass%, more preferably 5 to 70 mass%, and most preferably 10 To 60 mass% is particularly preferable. The solvent content may be adjusted depending on the desired thickness and the coating method. For example, when the application method is a spin coat or a slit coat, the content of the solvent in the above range of solid concentration is preferable. The amount is preferably 0.1% by mass to 50% by mass, more preferably 1.0% by mass to 25% by mass for a spray coat. By adjusting the amount of the solvent according to the coating method, the resin composition layer having a desired thickness can be uniformly formed.

The solvent may be one kind or two or more kinds. When two or more kinds of solvents are used, the total amount is preferably in the above range.

The content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide, Is preferably less than 5% by mass, more preferably less than 1% by mass, more preferably less than 0.5% by mass, and further preferably less than 0.1% by mass based on the total mass of the composition.

<< Increasing coloring >>

The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific actinic radiation and becomes an electron-excited state. The sensitizing dyes which are brought into the electron-excited state come into contact with a thermal base generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like to generate an action of electron transfer, energy transfer, heat generation and the like. As a result, the thermal base generator, photobase generator, thermal radical polymerization initiator and photopolymerization initiator are decomposed by chemical change to generate radicals, acids or bases. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Laid-Open Patent Publication No. 2016-027357, the contents of which are incorporated herein by reference. When the resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass relative to the total solid content of the resin composition desirable. The sensitizing dyes may be used singly or in combination of two or more.

<< chain transfer agent >>

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Advance, 3rd Edition (Polymer Science Society, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH and GeH in the molecule is used. These can produce radicals by hydrogen donating radical species of low activity, or after oxidation, by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5- Etc.) can be preferably used. When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition 1 to 5 parts by mass. The chain transfer agent may be one kind or two or more kinds. When two or more kinds of chain transfer agents are used, it is preferable that the total is in the above range.

<< Surfactant >>

Various surfactants may be added to the resin composition of the present invention from the viewpoint of further improving the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The following surfactants are also preferred.

(38)

When the resin composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the resin composition. The surfactant may be one kind or two or more kinds. When two or more kinds of surfactants are contained, the total amount thereof is preferably in the above range.

<< High Fatty Acid Derivatives >>

In order to prevent polymerization inhibition due to oxygen, a high fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention and may be localized on the surface of the composition during drying after application. When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. The higher fatty acid derivative may be one kind or two or more kinds. When two or more higher fatty acid derivatives are used, the total amount is preferably in the above range.

<< Other additives >>

The resin composition according to the present invention may contain various additives such as inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like in a range that does not impair the effect of the present invention Can be blended. When these additives are compounded, the total amount of the additives is preferably 3 mass% or less of the solid content of the resin composition.

<<< Restrictions on Other Contaminants >>>

The water content of the resin composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface properties.

The metal content of the resin composition in the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm from the viewpoint of insulation. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, it is preferable that the sum of these metals is in the above range.

As a method for reducing metal impurities which are not intended to be included in the resin composition, there is a method of selecting a raw material having a low metal content as a raw material constituting the resin composition, filtering the raw material constituting the resin composition, Polytetrafluoroethylene or the like, followed by distillation under conditions in which contemination is suppressed as much as possible.

In the resin composition of the present invention, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm from the viewpoint of wire corrosion resistance. Among them, those present in the halogen ion state are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The sum of the chlorine atom and the bromine atom, or the chloride ion and the bromine ion is preferably in the above range.

&Lt; Preparation of Resin Composition >

The resin composition can be prepared by mixing the respective components described above. The mixing method is not particularly limited, and can be performed by conventionally known methods.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as dust and fine particles in the resin composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be previously washed with an organic solvent. In the filter filtering step, a plurality of kinds of filters may be connected in series or in parallel. When plural kinds of filters are used, filters having different hole diameters and / or different materials may be used in combination. In addition, various materials may be filtered a plurality of times. In the case of performing filtration a plurality of times, it may be circulated filtration. Alternatively, filtration may be performed by pressurization. When the filtration is performed by pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using a sorbent material 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.

<Electronic device>

Next, an embodiment of an electronic device obtained by applying the method for producing a laminate of the present invention will be described. The electronic device 100 shown in Fig. 2 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked is arranged on the wiring board 120 have. Although the number of stacked semiconductor elements (semiconductor chips) is four in this embodiment, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. For example, the number of stacked semiconductor elements , 16 layers, and 32 layers. It may be a single layer.

The plurality of semiconductor elements 101a to 101d are all made of a semiconductor wafer such as a silicon substrate.

The uppermost semiconductor element 101a does not have a penetrating electrode, and an electrode pad (not shown) is formed on one surface thereof.

The semiconductor elements 101b to 101d have penetrating electrodes 102b to 102d, and connection pads (not shown) provided integrally on the penetrating electrodes are provided on both surfaces of each semiconductor element.

The stacked body 101 has a structure in which semiconductor elements 101a having no penetrating electrodes and semiconductor elements 101b to 101d having penetrating electrodes 102b to 102d are flip-chip connected.

That is, the connection pads on the semiconductor element 101a side of the semiconductor element 101b having the electrode pad of the semiconductor element 101a having no penetrating electrode and the penetrating electrode 102b adjacent thereto are electrically connected to the metal bump such as a solder bump And the connection pad on the other side of the semiconductor element 101b having the penetrating electrode 102b is connected to the semiconductor element 101b on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto. A connection pad, and a metal bump 103b such as a solder bump. The connection pad on the other side of the semiconductor element 101c having the penetrating electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the penetrating electrode 102d adjacent thereto, Or the like by a metal bump 103c.

An underfill layer 110 is formed in the gap between the semiconductor elements 101a to 101d and the semiconductor elements 101a to 101d are stacked via the underfill layer 110. [

The stacked body 101 is stacked on the wiring substrate 120. [

As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a substrate is used. As the wiring board 120 to which the resin substrate is applied, a multilayer copper clad laminate (multilayer printed wiring board) and the like can be given.

On one surface of the wiring board 120, a surface electrode 120a is provided.

An insulating layer 115 in which a re-wiring layer 105 is formed is disposed between the wiring substrate 120 and the layered body 101. The wiring substrate 120 and the layered body 101 are electrically connected to each other through the re- As shown in Fig. The insulating layer 115 is formed using the method for producing a laminate of the present invention. The insulating layer 115 may be a laminate of a multilayer interconnection structure as shown in Fig.

One end of the re-distribution layer 105 is connected to an electrode pad formed on the side of the re-distribution layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the re-distribution layer 105 is connected to the surface electrode 120a of the wiring substrate via a metal bump 103e such as a solder bump.

An underfill layer 110a is formed between the insulating layer 115 and the layered body 101. [ An underfill layer 110b is formed between the insulating layer 115 and the wiring board 120. [

&Lt; Method of manufacturing electronic device &

Next, a manufacturing method of the electronic device of the present invention will be described. The method for manufacturing an electronic device of the present invention includes the above-described method for producing a laminate of the present invention. In the method of manufacturing an electronic device of the present invention, it is preferable to manufacture a plurality of electronic devices under the same conditions of the preservation process.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it departs from the spirit thereof. In addition, "% " and " part " are on a mass basis unless otherwise specified. NMR is an abbreviation of nuclear magnetic resonance.

(Synthesis Example 1)

[Synthesis of polyimide precursor (P-1: polyimide precursor having no radical polymerizable group) from pyromellitic dianhydride, 4,4'-oxydianiline and benzyl alcohol]

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 캜 for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 ml of N-methylpyrrolidone, Lt; / RTI &gt; The suspension was heated at 100 占 폚 for 3 hours. A transparent solution was obtained after several minutes from the start of heating. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10 ℃, while maintaining the temperature at -10 ± 4 ℃ was added SOCl ₂ of 16.12g (135.5 mmol) for 10 min. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Subsequently, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C for 20 minutes. The reaction mixture was then stirred at room temperature overnight. Subsequently, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was filtered, put into 4 liters of water, stirred again for 30 minutes, and filtered again. Subsequently, the obtained polyimide precursor was dried at 45 캜 for 3 days under reduced pressure to obtain a polyimide precursor (P-1) containing the repeating unit represented by the following formula.

[Chemical Formula 39]

(Synthesis Example 2)

[Synthesis of polyimide precursor (P-2: polyimide precursor having a radically polymerizable group) from pyromellitic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]

14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 캜 for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone and 10.7 g Of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 DEG C for 18 hours to obtain a diastereomer of pyromellitic acid and 2-hydroxyethyl methacrylate . Subsequently, the resulting diester was chlorinated by SOCl ₂ , and then converted into a polyimide precursor with 4,4'-oxydianiline in the same manner as in Synthesis Example 1, and the same procedure as in Synthesis Example 1 was repeated, To obtain a polyimide precursor (P-2).

(40)

(Synthesis Example 3)

[Synthesis of polyimide precursor (P-3: polyimide precursor having radically polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone , 10.7 g of pyridine and 140 g of diglyme were mixed and stirred at a temperature of 60 DEG C for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate . Subsequently, the resulting diester was chlorinated by SOCl ₂ , and then converted into a polyimide precursor with 4,4'-oxydianiline in the same manner as in Synthesis Example 1, and the same procedure as in Synthesis Example 1 was repeated, To obtain a polyimide precursor (P-3).

(41)

(Synthesis Example 4)

[Synthesis of acrylic polymer (P-6)] [

(153.2 mmol) of benzyl methacrylate, 20 g (157.3 mmol) of N-isopropyl methacrylamide, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, V-601, manufactured by Wako Pure Chemical Industries, Ltd.) (3.5 g, 15.4 mmol) and 300 g of 3-methoxy-2-propanol were mixed. The mixed solution was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75 占 폚 in a nitrogen atmosphere over 2 hours. After completion of the dropwise addition, the mixture was stirred at 75 占 폚 for 2 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was poured into 5 liters of water to precipitate the polymer, and the mixture was stirred at a speed of 5000 rpm for 15 minutes. The acrylic resin was filtered, put into 4 liters of water again, stirred for another 30 minutes, and then filtered again. Subsequently, the obtained acrylic resin was dried at 45 캜 for 3 days under reduced pressure to obtain an acrylic polymer (P-6) represented by the following formula.

(42)

&Lt; Preparation of Photosensitive Resin Composition >

The following components were mixed to prepare a uniform solution to prepare a coating liquid for the photosensitive resin composition.

(Furtherance)

Resin: The mass parts

Radical Polymerizable Compound: The mass part

Photo radical polymerization initiator: The mass part

Silane coupling agent: The mass part

Antirust agent: The mass part

Polymerization inhibitor: The mass part

Base generator: The mass part

Solvent 1 (dimethyl sulfoxide): 100 parts by mass

Solvent 2 (? -Butyrolactone): 25 parts by mass

[Table 6]

Abbreviations given in the table are as follows.

(Suzy)

P-1 to P-3: The polyimide precursors (P-1) to (P-3) synthesized in Synthesis Examples 1 to 3,

P-5: Matrimid 5218 (Huntsman Corporation, closed loop polyimide)

P-6: An acrylic polymer (P-6) (acrylic resin) synthesized in Synthesis Example 5

P-7: Polymethyl methacrylate (Mw = 15000, manufactured by Sigma-Aldrich Japan Kogyo Co., Ltd.)

(Radical Polymerizable Compound)

B-1: SR209 (tetraethylene glycol diacrylate manufactured by Satomaru Co., Ltd.)

B-2: NK Ester A-9300 (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., ethoxylated isocyanuric acid triacrylate)

B-3: A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

B-4: A-DPH (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., dipentaerythritol hexaacrylate)

(Photo radical polymerization initiator)

C-1: IRGACURE OXE 01 (manufactured by BASF, oxime compound)

C-2: IRGACURE OXE 02 (manufactured by BASF, oxime compound)

C-3: IRGACURE-784 (a metallocene compound made by BASF)

C-4: ADEKA ALEX NCI-831 (manufactured by ADEKA, oxime compound)

(Silane coupling agent)

D-1: KBM-602 (a silane compound having an amino group, manufactured by Shin-Etsu Chemical Co., Ltd.)

D-2: 2 - ((3- (triethoxysilyl) propyl) carbamoyl) benzoic acid (a silane compound having a carboxyl group, manufactured by Aquila Pharmatech LLC)

D-3: Triethoxysilylpropyl maleamic acid (a silane compound having a carboxyl group, manufactured by Gelest, Inc)

(Rust inhibitor)

E-1: KEMITEC BT-C (manufactured by KEMIPRO Co., Ltd., 1,2,3-benzotriazole)

E-2: 1HT (manufactured by Toyobo Co., 1 H-tetrazole)

E-3: P5T (5-phenyl-1H-tetrazole, manufactured by Toyobo Co., Ltd.)

(Polymerization inhibitor)

F-1: 4-methoxyphenol

F-2: p-benzoquinone

F-3: 1-nitroso-2-naphthol

(Base generator)

A-1, A-21, A-40: A compound of the following structure (thermal base generator)

A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.), a photoacid generator This compound is also a compound which is decomposed by heating to generate a base, that is, a thermal base generator.

(43)

&Lt; Preparation of laminate >

Each of the photosensitive resin compositions was subjected to pressure filtration through a filter having a pore width of 0.8 m and then layered on a silicon wafer by a spin coating method and dried at 100 DEG C for 5 minutes using a hot plate, Thereby forming a resin composition layer. Next, after the storage step (PCD step) was carried out at the time and temperature described in the following table, the photosensitive resin composition layer was exposed to light with an exposure energy of 500 mJ / cm ² using a stepper (Nikon NSR 2005 i9C). Next, the photosensitive resin composition layer after the exposure was subjected to a preservation step (PED step) at the time and temperature described in the following table, and then developed for 60 seconds using cyclopentanone to form a hole having a diameter of 10 m. Next, a preservation step (PDD step) was performed at the time and temperature described in the following table, and then the resin layer (pattern) was formed by heating at 230 DEG C for 3 hours in a nitrogen atmosphere. Next, the resin layer (pattern) after the heating was cooled to room temperature, and the copper layer was subjected to a preservation step (PBD step) at the time and temperature described in the following table. Thereafter, copper plating treatment was performed to form a copper thin film And a laminate 1 was formed.

Each preservation step was carried out by standing on a clean thermo-hygrostat (PCR-3J, made by Espec Co., Ltd.) adjusted to the set temperature described in the following table.

Next, the copper thin film of the layered product 1 was irradiated with oxygen plasma, and then the application of the photosensitive resin composition, exposure, development, heating and each preservation step were carried out, and then copper plating treatment was carried out, A copper thin film of 5 mu m was formed to obtain a laminate 2.

Next, the copper thin film of the layered product 2 was irradiated with an oxygen plasma, and then the application of the photosensitive resin composition, exposure, development, heating, and each preservation step were performed, and then copper plating treatment was carried out. A copper thin film of 5 mu m was formed to obtain a laminate 3.

[Table 7]

The storage time in each of the conditions described in the above table is the elapsed time since the surface temperature reached the set temperature. The fluctuation range of the surface temperature in each preservation step was 5 DEG C or less. In addition, the average surface temperature in each preservation step was almost the same as the set temperature.

<Evaluation>

[Peeling defect (evaluation 1)]

The laminate 2 was cut in the vertical direction to observe a section of 5 mm in width, and the presence or absence of peeling between the resin layer / resin layer and the copper / resin layer was confirmed. If there is no occurrence of peeling, it exhibits excellent adhesion, which is a preferable result.

A: No peeling occurred

B: 1 to 2 peeling occurrences

C: 3 to 5 peeling occurrences

D: 6 or more occurrences of peeling

[Defective peeling (Evaluation 2)]

The laminate 3 was cut in the vertical direction to observe a section of 5 mm in width, and the presence or absence of peeling between the resin layer / resin layer and between the copper / resin layer was confirmed. If there is no occurrence of peeling, it exhibits excellent adhesion, which is a preferable result.

A: No peeling occurred

B: 1 to 2 peeling occurrences

C: 3 to 5 peeling occurrences

D: 6 or more occurrences of peeling

[Limit resolution (evaluation 3)]

The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure was performed by i-line, and exposure was carried out using a photomask of a fuse box at a wavelength of 365 nm and an exposure energy of 200 mJ / cm ² at intervals of 1 μm from 5 μm to 25 μm. The exposed photosensitive resin composition layer was developed using cyclopentanone and propylene glycol methyl ether acetate as a developer. Specifically, cyclopentanone was sprayed on the exposed photosensitive resin composition layer, followed by spraying propylene glycol methyl ether acetate for 60 seconds. The line width at which the silicon wafer was exposed at the bottom of the fuse box was evaluated based on the following criteria. The smaller the line width is, the smaller the width of the metal wiring formed in the subsequent plating step becomes, which is a preferable result. The measurement limit is 5 μm. The results are shown in the table.

A: 5 占 퐉 or more and 8 占 퐉 or less

B: more than 8 m but not more than 10 m

C: more than 10 m but not more than 15 m

D: more than 15 μm

[Table 8]

As shown in the above table, in the example in which the preservation step was performed, a laminate having good adhesion could be produced. In addition, the photosensitive resin compositions of Compositions 1 to 12 using a polyimide precursor as a resin had a high limit resolution, and the laminate of Examples 1 to 33, 36, and 37 using this photosensitive resin composition exhibited a finer can do.

100: electronic device
101a to 101d: semiconductor elements
101: laminate
102b to 102d: through electrode
103a to 103e: metal bump
105: rewiring layer
110, 110a, 110b: underfill layer
115: Insulating layer
120: wiring board
120a: surface electrode
201 to 204: Resin layer
301 to 303: metal layer
401 to 403: Home
500: laminate

Claims (16)

A step of forming a photosensitive resin composition layer by applying a photosensitive resin composition comprising a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator to a support to form a photosensitive resin composition layer and,
An exposure step of exposing the photosensitive resin composition layer in a pattern shape,
A developing step of developing the photosensitive resin composition layer to form a pattern;
A heating step of heating the pattern;
And a metal layer forming step of forming a metal layer on the pattern after heating,
At least one of the steps of forming the photosensitive resin composition layer and the exposure step, between the exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step, , And then carrying out a preservation step for preservation in that state for 5 minutes or more. The method according to claim 1,
And the preserving step is performed between the exposure step and the developing step. The method of claim 2,
The storage step performed between the exposure step and the developing step satisfies the following formula:
^{5≤t1 <(10 -. 0.036 ×} T1 +12 3) × 60
T1 is an average surface temperature in the preservation step carried out between the exposure step and the developing step, and the unit is K; t1 is the time of the storage step performed between the exposure step and the developing step, and the unit is minute. The method according to any one of claims 1 to 3,
Wherein the preserving step is carried out between the step of forming the photosensitive resin composition layer and the step of exposing. The method of claim 4,
The storage step performed between the photosensitive resin composition layer forming step and the exposure step satisfies the following formula:
^{5≤t2 <(10 -. 0.031 ×} T2 +10 7) × 60
T2 is an average surface temperature in the storage step performed between the photosensitive resin composition layer forming step and the exposure step, and the unit is K; t2 is the time of the preservation step performed between the photosensitive resin composition layer forming step and the exposure step, and the unit is minutes. The method according to any one of claims 1 to 5,
And the preserving step is performed between the developing step and the heating step. The method of claim 6,
The storage step performed between the developing step and the heating step satisfies the following formula:
T3 < (10 ^{- 0.02 x T3 +} 8.0) x 60
T3 is the average surface temperature in the storage step carried out between the developing step and the heating step, and the unit is K; t3 is the time of the storage step performed between the developing step and the heating step, and the unit is minute. The method according to any one of claims 1 to 7,
And the preserving step is performed between the heating step and the metal layer forming step. The method according to any one of claims 1 to 8,
Wherein the resin in the photosensitive resin composition is a polyimide precursor,
Wherein the polyimide precursor comprises a radically polymerizable group or the photosensitive resin composition contains a radically polymerizable compound other than the polyimide precursor. The method according to any one of claims 1 to 9,
Wherein the polyimide precursor comprises a repeating unit represented by the following formula (1);
Equation (1)
[Chemical Formula 1]

In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. The method of claim 10,
Wherein at least one of R ²³ and R ²⁴ in the formula (1) contains a radically polymerizable group. The method according to claim 10 or 11,
Wherein R &lt; ²² &gt; in the formula (1) is a tetravalent group containing an aromatic ring. The method according to any one of claims 1 to 12,
The step of forming the photosensitive resin composition layer, the step of exposing, the step of developing, the step of heating, and the step of forming a metal layer are performed in this order on the pattern after the metal layer forming step, and the step of forming the photosensitive resin composition layer and the step of exposing A series of cycles for carrying out the preservation step in at least one of the above exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step is referred to as a second cycle Cycle or more. The method according to any one of claims 1 to 13,
A method for producing a laminate of a multilayer wiring structure. A step of forming a photosensitive resin composition layer by applying a photosensitive resin composition comprising a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator to a support to form a photosensitive resin composition layer and,
An exposure step of exposing the photosensitive resin composition layer in a pattern shape,
A developing step of developing the photosensitive resin composition layer to form a pattern;
A heating step of heating the pattern;
And a metal layer forming step of forming a metal layer on the pattern after heating,
At least one of the steps of forming the photosensitive resin composition layer and the exposure step, between the exposure step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step, And then performing a preservation step of preserving the state for 5 minutes or longer. 16. The method of claim 15,
And a plurality of electronic devices are manufactured under the same conditions of the preservation process.

Images