WO2019163860A1

WO2019163860A1 - Film production method, laminate production method, semiconductor device production method, and film formation composition

Info

Publication number: WO2019163860A1
Application number: PCT/JP2019/006428
Authority: WO
Inventors: 沢野　充; 慶福原; 誠也増田; 嶋田　和人
Original assignee: 富士フイルム株式会社
Priority date: 2018-02-23
Filing date: 2019-02-21
Publication date: 2019-08-29
Also published as: KR20200110402A; TW201938644A; JPWO2019163860A1; KR102433579B1; CN111819306A

Abstract

This film production method includes a step for performing slit coating on a member, which at least partially contains a metal, by using a composition containing: a polyimide precursor; at least two solvents having different solubilities at 23°C for the polyimide precursor; and at least one selected from the group consisting of a surfactant and a plasticizer. The present invention further pertains to a laminate production method, a semiconductor device production method and a film formation composition that relate to said film production method.

Description

Film manufacturing method, laminate manufacturing method, semiconductor device manufacturing method, and film forming composition

The present invention relates to a film manufacturing method, a laminate manufacturing method, a semiconductor device manufacturing method, and a film forming composition.

Polyimide resins are excellent in heat resistance and insulation, and thus are applied to various uses. Although the use is not particularly limited, when a semiconductor device for mounting is taken as an example, it can be used as a material for an insulating film or a sealing material, or as a protective film thereof. It is also used as a base film and coverlay for flexible substrates.
The above polyimide resin generally has low solubility in a solvent. Therefore, a method of dissolving in a solvent in a state of a polyimide precursor before cyclization is often used. Thereby, the excellent handleability can be realized, and when manufacturing each product as described above, it can be applied and processed in various forms on a substrate or the like. Thereafter, the polyimide precursor can be heated to form a cured product. In addition to the high performance possessed by polyimide resin, its industrial application development is increasingly expected from the viewpoint of excellent adaptability in manufacturing.

On the other hand, Patent Document 1 describes slit coating of a resin composition containing a surfactant.

JP 2013-243121 A

Here, as described in Patent Document 1, a technique for forming a composition containing a polyimide precursor into a film by slit coating (slit coating) is known. However, it has been found that when the object of slit coating of the polyimide precursor composition contains a metal on its surface, the surface of the film may become so-called “Yuzu skin”.

An object of the present invention is to solve the above-mentioned problems, and even when a coating film is formed on a metal surface, it is possible to achieve a good surface shape by suppressing the occurrence of “Yuzu skin”. An object of the present invention is to provide a method for producing a film using a slit coat, a method for producing a laminate, a method for producing a semiconductor device, and a film forming composition suitable for use in these production methods.

As a result of investigation by the present inventors based on the above problems, when a composition containing a polyimide precursor is applied in a layer form by a slit coating method, Benard cells are generated during drying, and the surface becomes distorted. I found it. And in the composition containing the polyimide precursor (coating liquid for film formation), as the solvent, at least two kinds of solvents having different solubility at 23 ° C. with respect to the polyimide precursor are used. It has been found that the above problem can be solved by blending at least one selected from the group consisting of plasticizers.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <23>.

<1> Using a composition comprising a polyimide precursor, at least two solvents having different solubility at 23 ° C. with respect to the polyimide precursor, and at least one selected from the group consisting of a surfactant and a plasticizer, A method for producing a film, comprising a step of slit coating on a member, wherein the member contains a metal at least in part.
<2> The method for producing a film according to <1>, wherein the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
<3> The method for producing a film according to <1> or <2>, including a head cleaning step of cleaning the nozzle head with a cleaning liquid after the step of performing the slit coating.
<4> The step of performing the slit coating includes a head standby step, wherein the nozzle head is immersed in an immersion liquid in the head standby process, and the immersion liquid has a composition that is 90% by mass or more in common with the cleaning liquid. The method for producing a film according to <3>, wherein
<5> The method for producing a film according to <3> or <4>, wherein the cleaning liquid contains a solvent having the highest solubility at 23 ° C. of the polyimide precursor among the at least two kinds of solvents.
<6> The film production according to any one of <3> to <5>, wherein the cleaning liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C. among the at least two solvents. Method.
<7> The method for producing a film according to <4>, wherein the immersion liquid contains a solvent having the highest solubility at 23 ° C. of the polyimide precursor among the at least two kinds of solvents.
<8> The method for producing a film according to <4> or <7>, wherein the immersion liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two solvents.
<9> The method for producing a film according to any one of <1> to <8>, comprising an exposure step of exposing the film formed by the slit coating and a development step of developing the exposed film.
<10> The method for producing a film according to any one of <1> to <9>, further including a heating step of heating the film.
<11> A method for producing a laminate, wherein the method for producing a film according to any one of <1> to <10> is performed a plurality of times.
<12> The method for producing a laminate according to <11>, including a step of applying a metal layer to the film.
<13> A method for manufacturing a semiconductor device, wherein a chip is arranged on a film manufactured by the method according to any one of <1> to <10>.
<14> A method for producing a semiconductor device, in which a chip is arranged on a laminate produced by the method according to <11> or <12>.
<15> A film-forming composition used in the production method according to any one of <1> to <10>, wherein the polyimide precursor and the polyimide precursor have different solubility at 23 ° C. A film-forming composition comprising two kinds of solvents and at least one selected from the group consisting of a surfactant and a plasticizer.
<16> The film forming composition according to <15>, wherein the polyimide precursor is a condensate of a dicarboxylic acid and a diamino compound.
<17> Among the at least two solvents, the solvent having the highest solubility of the polyimide precursor is a sulfoxide or lactam solvent, and of the at least two solvents, the solubility of the polyimide precursor is the highest. The film forming composition according to <15> or <16>, wherein the low solvent is a solvent of ketones or lactones.
<18> Among the at least two solvents, the solubility of the polyimide precursor is higher than the average value below, and among the at least two solvents, the solubility of the polyimide precursor is below the average value below. The film forming composition according to any one of <15> to <17>, wherein the ratio of the total mass of the low solvent is 10:90 to 45:55;
The average value is an average value of the solubility of the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solubility of the polyimide precursor having the lowest solubility at 23 ° C.
<19> The film forming composition as described in any one of <15> to <18>, wherein the surfactant contains a fluorine atom.
<20> The film forming composition according to <19>, wherein the surfactant is a compound having a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
<21> The film-forming composition according to any one of <15> to <20>, wherein the content of the surfactant is 0.005 to 2% by mass in the solid content.
<22> The film-forming composition according to any one of <15> to <21>, wherein the plasticizer is an epoxidized oil.
<23> The film forming composition according to any one of <15> to <22>, wherein the content of the plasticizer is 0.005 to 2% by mass in the solid content.

According to the present invention, even when a resin coating film is formed on the metal surface in the slit coat, it is possible to suppress the occurrence of “Yuzu skin” and achieve a good surface shape.

It is process explanatory drawing (1) for demonstrating preferable embodiment of the slit coat applied in this invention with a typical side view. It is process explanatory drawing (2) for demonstrating preferable embodiment of the slit coat applied in this invention with a typical side view. It is process explanatory drawing (3) for demonstrating preferable embodiment of the slit coat applied in this invention with a typical side view.

The description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) acryl” represents both “acryl” and “methacryl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion 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, for example, HLC-8220GPC (manufactured by Tosoh Corp.), guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using any one or more of Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
The shape, dimensions, number, arrangement location, and the like exemplified in the drawings are arbitrary and are not limited.

The method for producing a film of the present invention includes a polyimide precursor, at least two solvents having different solubility in a polyimide precursor at 23 ° C., and at least one selected from the group consisting of a surfactant and a plasticizer. It includes a step of performing slit coating on a member containing a metal at least in part using the composition. As a result, even when a coating film is formed on the metal surface in the slit coat, it is possible to suppress the occurrence of “yuzu skin” and achieve a good surface shape (gloss).
The polyimide precursor is cured by heating after forming a coating film. That is, it was speculated that the coating film was in a fluid liquid state at the stage of application, and as a result, it had been distorted. And it was estimated that it was important to consider the following points as a result in order to suppress yuzu skin.
(1) In order to suppress convection at an early stage during drying, a solvent having a low solubility is employed in addition to a solvent having a high solubility, and
(2) Adopt a surfactant to lower the surface tension of the coating film, or (3) Add a plasticizer to avoid the surface drying first and internal convection continuing and as above By using two or more solvents having different solubilities and using at least one selected from the group consisting of a surfactant and a plasticizer, the skin was successfully suppressed and the surface condition was successfully improved. . Furthermore, the adhesion between the polyimide resin layer and the metal (for example, metal layer) has been successfully improved. In particular, by using a predetermined surfactant, it has succeeded in obtaining excellent adhesion with copper (for example, a copper layer).
The present invention will be described in detail below.

<Slit coat>
FIG. 1 is a process explanatory diagram (1) for explaining a preferred embodiment of a slit coat applied in the present invention in a schematic side view. The coating apparatus 100 of this embodiment includes a transport unit 23 that transports the substrate 30 and a support stage (not shown) that supports the substrate from below. A resist (resin) 21a is discharged from the nozzle head 21 to the substrate 30 through a slit-like nozzle, and the substrate 30 is conveyed in the direction d3 (slit coating process). The conveyance unit 23 can be configured by a plurality of conveyance rollers and a conveyance roller driving unit that rotates the conveyance rollers. The nozzle head 21 can be lifted up and down in accordance with the timing at which the transport unit transports the substrate 30. Similarly, a support stage (not shown) can also be moved and retracted from directly below the nozzle head. At this time, it is possible to wait the nozzle head and wait for the next substrate to be sent (head waiting step). The nozzle head immersion process (immersion process process) and the cleaning process (head cleaning process) described below may be performed in the head standby process during the slit coating process or after the slit coating process.

In the apparatus 100 of the present embodiment, the nozzle head cleaner 22 is disposed immediately below the nozzle head. When the discharge of the resin onto the substrate is completed, the nozzle head is lowered (d1) along a direction perpendicular to the coating surface, and the nozzle head 21 is immersed in the immersion liquid provided in the nozzle head cleaner 22 (FIG. 2). The time for immersing the nozzle head in the immersion liquid in the cleaner is, for example, preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and further preferably 0.5 minutes or more. The upper limit is preferably 10 minutes or less, more preferably 8 minutes or less, and even more preferably 5 minutes or less. Thereby, the tip of the nozzle head 21 can be cleaned.

FIG. 3 is a side view of the apparatus for explaining a head maintenance process different from those shown in FIGS. 1 and 2 and shows a mode of maintenance (cleaning) of the nozzle head. The apparatus of this embodiment includes a roller 24 that rotates in the d2 direction. The roller bat 25 is filled with a cleaning liquid 25a so that the lower part of the roller 24 is immersed. The apparatus 100 of this embodiment is further provided with a liquid draining blade 25b. The roller 24 and the roller butt 25 constitute a maintenance unit 26. The maintenance unit can be moved up and down in a direction perpendicular to the substrate surface. The apparatus according to the present embodiment includes such a maintenance unit, so that maintenance (cleaning) of the nozzle head 21 can also be performed by raising the maintenance unit 26 d4 without lowering the nozzle head 21 d5 in the maintenance process. Can be performed. In the maintenance unit, the liquid flowing from d5 is switched to the cleaning liquid. The time for which the cleaning liquid flows through the nozzle head is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and further preferably 5 minutes or longer. As an upper limit, it is preferable that it is 120 minutes or less, It is more preferable that it is 60 minutes or less, It is further more preferable that it is 30 minutes or less. Thereby, the nozzle head 21 can be cleaned.

In the present invention, as described above, the slit coating step preferably includes a head standby step. In the head standby step, the head is preferably immersed in the immersion liquid. The immersion liquid is preferably a liquid having a composition that is 90% by mass or more in common with the cleaning liquid, more preferably a liquid having a composition that has 95% by mass or more in common, and even more preferably the same composition.
The immersion liquid and the cleaning liquid are each preferably a liquid having a composition that is 90% by mass or more in common with the solvent in the film-forming composition with respect to the type and mixing ratio of the compound, and 95% by mass or more. More preferably, it is a liquid, and it is further more preferable that it is the same composition.
The cleaning liquid preferably contains a solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents contained in the film-forming composition. Moreover, it is preferable that a washing | cleaning liquid contains the solvent with the lowest solubility in 23 degreeC of a polyimide precursor among the at least 2 types of solvents contained in the composition for film formation. Furthermore, among at least two kinds of solvents contained in the film-forming composition, it contains both the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solvent having the lowest solubility of the polyimide precursor at 23 ° C. preferable.
The immersion liquid preferably also contains a solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two solvents contained in the film-forming composition. Moreover, it is preferable that an immersion liquid contains the solvent with the lowest solubility at 23 degreeC of a polyimide precursor among the at least 2 types of solvents contained in the composition for film formation. Furthermore, among at least two kinds of solvents contained in the film-forming composition, it contains both the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solvent having the lowest solubility of the polyimide precursor at 23 ° C. preferable.

In addition, regarding the slit coat and the apparatus applicable thereto, JP 2009-070973 A can be referred to, and the matters described therein are incorporated in this specification.

<Film forming composition>
<< Polyimide precursor >>
As a polyimide precursor, it is preferable that the repeating structural unit (structural unit) represented by following formula (1) is included.

A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently Represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² are each independently an oxygen atom or NH, preferably an oxygen atom.

<<< R ¹¹¹ >>>
R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group composed of an aromatic group, a heteroaromatic group, or a combination thereof, and has 2 to 20 carbon atoms. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. An aromatic group having 6 to 20 carbon atoms is more preferable.
R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. One type of diamine may be used, or two or more types may be used.
Specifically, the diamine is a straight chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.

In the formula, A represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO ₂ —, — NHCO— and a group selected from these combinations are preferable. 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 — is more preferable, and —CH ₂ —, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —C (CH ₃₎ 2 _- and more preferably a divalent radical selected from the group consisting of.

Specific examples of the diamine include 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 and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 ' -And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, , 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino Paraterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenyl Sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenyl) benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′- Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4 -Aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diamino Anthraquinone, 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9′-bis (4-aminophenyl) fluorene, 4 4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-meta Phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid Ester, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis ( -Aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetra Decafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (4-Aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane , Parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4′-bis (4-amino) -2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone 4,4′-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3, 3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2 ′, 5,5 ′, 6 And at least one diamine selected from 4,6′-hexafluorotolidine and 4,4′-diaminoquaterphenyl.

Further, diamines (DA-1) to (DA-18) shown below are also preferable.

A preferred example is a diamine having at least two alkylene glycol units in the main chain. Preferred is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine containing no aromatic ring. Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark). ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2 -Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. Not.
Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

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

R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ^0- . However, Ar ⁰ is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L ⁰ is a group of the above A It is synonymous and the preferable range is also the same. Ar ⁰ is preferably a phenylene group.

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

R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or A trifluoromethyl group.
^Examples of the monovalent organic group represented by R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.

<<< R ¹¹⁵ >>>
R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.

R ¹¹² has the same meaning as A, and the preferred range is also the same.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1, -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride And at least one selected from alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.

<<< R ¹¹³ and R ¹¹⁴ >>>
R ¹¹³ and R ¹¹⁴ in Formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom) To 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH ₂ CH (OH) CH ₂ —, and ethylene group, propylene group, trimethylene group, and —CH ₂ CH (OH) CH ₂ — are more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

Preferred embodiments of the polyimide precursor include aliphatic groups, aromatic groups, arylalkyl groups, etc. having 1, 2, or 3, preferably 1, acid groups as the monovalent organic group of R ¹¹³ or R ¹¹⁴ Is mentioned. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.
As the monovalent organic group represented by ^R113 or ^R114, a substituent that improves the solubility of the developer is preferably used.
R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group. Isopropyl group, isobutyl 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 cyclic alkyl group. Examples of the monocyclic 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 alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene. Ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring , Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, fluorine Nantororin ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. A benzene ring is most preferred.

The polyimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1). Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A).

A ¹¹ and A ¹² each represent an oxygen atom or NH; R ¹¹¹ and R ¹¹² each independently represent a divalent organic group; and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent group. An organic group is represented, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a radical polymerizable group, and is preferably a radical polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently synonymous with A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), and the preferred ranges are also the same. is there.
R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

In the polyimide precursor, the repeating structural unit represented by the formula (1) may be one type or two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included. The polyimide precursor may also contain other types of structural units in addition to the structural unit of the above formula (1).

As an embodiment of the polyimide precursor, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the structural units is a structural unit represented by the formula (1) is exemplified. The As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The polyimide precursor is a condensate of dicarboxylic acid or dicarboxylic acid derivative and diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used for the reaction. One or more organic solvents may be used.
The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

In producing the polyimide precursor, it is preferable to include a step of depositing a solid. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble.

The proportion of the polyimide precursor in the film-forming composition is preferably 60% by mass or more of the component (solid content) excluding the solvent, more preferably 70% by mass or more, and 75% by mass or more. Is more preferably 99% by mass or less, and more preferably 95% by mass or less.
The film forming composition may contain only one type of polyimide precursor or two or more types of polyimide precursors. When 2 or more types are included, the total amount is preferably within the above range.

<< Solvent >>
The composition (film forming composition) used in the film production method contains at least two solvents having different solubility at 23 ° C. in the polyimide precursor as the solvent. Specifically, it is preferable to use a mixed solvent of at least a solvent A having higher solubility with respect to the polyimide precursor and a solvent B having lower solubility at 23 ° C. as the solvent. The solubility is defined as the amount (g) of the polyimide precursor that is soluble in 100 g of a solvent at 23 ° C.
When there are three or more solvents, the average value of the solubility of the solvent having the highest solubility and the solubility of the solvent having the lowest solubility is obtained. Are classified as Solvent B. Furthermore, when there are three or more solvents, the solvent having the highest solubility is preferably solvent A, and the solvent having the lowest solubility is preferably solvent B.
The difference in solubility between the solvent A and the solvent B is preferably 10 g or more, more preferably 15 g or more, and further preferably 20 g or more. The upper limit is not particularly defined, but can be, for example, 50 g or less. By setting it as such a structure, the convection in the early stage during drying of a coating film can be suppressed more effectively.

The boiling point of the solvent A is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 130 ° C. or higher. The upper limit is preferably 230 ° C. or lower, more preferably 210 ° C. or lower, and further preferably 190 ° C. or lower. By setting it as such a structure, it exists in the tendency for the surface shape after application | coating to become more uniform.
The boiling point of the solvent B is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. The upper limit is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and further preferably 210 ° C. or lower. By setting it as such a structure, it exists in the tendency for the surface shape after application | coating to become more uniform.
It is preferable that the solvent A and the solvent B have a predetermined difference in boiling points. The difference in boiling points is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. Moreover, it is preferable that it is 80 degrees C or less. By adopting such a configuration, it becomes possible to keep the surface shape more uniform for a longer time with the solvent B.
In the present specification, the boiling point means a temperature at which boiling occurs at 1013.25 hPa.

The solvent is preferably an organic solvent.
Examples of the solvent classified as solvent A include sulfoxides, amides, and lactams, and sulfoxides are preferred.
Examples of the solvent classified as the solvent B include esters, ethers, lactones, ketones, aromatic hydrocarbons and the like, among which lactones and ketones are preferable, and ketones are more preferable.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and lactones (γ -Butyrolactone, ε-caprolactone, δ-valerolactone), alkyl oxyacetates (eg methyl alkyloxyacetate, alkyloxyethyl acetate, butyl oxyoxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy) Methyl acetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate) , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, 2-alkyloxypropion) Ethyl, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)) Methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , Pyruvic acid Chill, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl and 2-oxobutanoate are mentioned as preferred.
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 Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
Preferable examples of amides include lactams (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone), N, N-dimethylacetamide, N, N-dimethylformamide and the like.

The content of the solvent is preferably such that the total solid concentration of the film-forming composition is 1 to 80% by mass, more preferably 1 to 60% by mass, and 5 to 40% by mass. The amount is more preferably 5% to 35% by weight.
The preferred range for each solvent is as follows. The solvent A (based on the total mass when there are plural types) is preferably 1 to 80% by mass in the film-forming composition, and preferably 1 to 60% by mass. More preferred is 5 to 40% by mass, still more preferred is 5 to 30% by mass. Solvent B (based on the total mass when there are plural kinds) is preferably 3 to 90% by mass, more preferably 6 to 80% by mass in the film-forming composition, and 10 to 60% by mass. More preferably, it is more preferably 15 to 50% by mass.
The mass ratio of the solvent A and the solvent B (when there are plural types, the total mass basis) is preferably 10:90 to 45:55, more preferably 15:85 to 40:60, and 20:80 More preferably, it is ˜30: 70.

<< Surfactant >>
The film-forming composition preferably contains a surfactant.
The surfactant is preferably a surfactant containing a fluorine atom, preferably a nonionic or anionic surfactant containing a fluorine atom, and a nonionic or anionic surfactant containing a fluorine atom. More preferably, it is an oligomer or polymer surfactant. The surfactant preferably contains a fluoroalkylene group, and more preferably contains a perfluoroalkyl group.
The surfactant is preferably soluble in water. The term “soluble” as used herein means that the solubility at 23 ° C. is 0.05% by mass or more. Further, the surfactant is preferably dissolved in water by 0.1% by mass or more at 23 ° C., more preferably by 0.5% by mass or more, and further preferably by 1% by mass or more. As an upper limit, it is practical that it is 5 mass% or less.
The surfactant may contain at least one of a hydrophilic group, a lipophilic group, and an ultraviolet reactive group in the molecule.
Especially, in this invention, it is preferable that it is a perfluoroalkyl group containing carboxylate (anionic type) from a viewpoint of improving moisture resistance. The surfactant is preferably soluble in water or slightly soluble (for example, 0.1% by mass or more), but is insoluble in hydrocarbon solvents (for example, hexane and toluene). The surface tension of a 0.1% by mass solution with respect to water is preferably 10 mN / m or more, and more preferably 15 mN / m or more. The upper limit is practically 50 mN / m or less. The surface tension of a 0.1% solution with respect to PGME (propylene glycol monomethyl ether) is preferably more than 25 mN / m, and more preferably 26 mN / m or more. The upper limit is practically 70 mN / m or less.

Specific examples of the fluorosurfactants are trade names of Florinert F-C430, Florinato F-C431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F-142D, Megafac F-171 , Megafuck F-172, Megafuck F-173, Megafuck F-177, Megafuck F-183, Megafuck F-410, Megafuck F-444, Megafuck F-470, Megafuck F-471, Mega Fuck F-478, Mega Fuck F-479, Mega Fuck F-480, Mega Fuck F-482, Mega Fuck F-484, Mega Fuck F-484, Mega Fuck F-486, Mega Fuck F-487, Mega Fuck F -489, Megafuck F-553, Megafuck F-554, Megafuck F- 56, Megafuck F-557, Megafuck F-569, Megafuck F-575, Megafuck F-780F, Megafuck F-781F, Megafuck R30 (above DIC Corporation); F Top EF301, F Top EF303, Ftop EF351, Ftop EF352 (above, Shin-Akita Kasei Co., Ltd.); Surflon S381, Surflon S382, Surflon SC101, Surflon SC105 (above, Asahi Glass Co., Ltd.); E5844 (Daikin Fine Chemical Co., Ltd.) BM-1000, BM-1100 (manufactured by BMC Chemie), and the like.

In terms of the above-mentioned DIC MegaFac series surfactant, the higher the hydrophilicity, the higher the fluorine atom content. The hydrophilic order is shown in part as follows: F-410> F-444> F-430, F-510, F-511, F-569, F-553, F-477, F-556 >> The order is F-554. Regarding the fluorine atom content, the order of F-430> F-410, F-510, F-511> F-444 >> F-569, F-553, F-554, F-477, F-556 and Become. In the hydrophilicity and fluorine atom content, at least one is preferably the left side (greater than) >>, and in both cases, the left side (greater than) >> is preferable.

Among the surfactants, Megafac F-410 and F-444 (both trade names) showed good results in the adhesion test after PCT performed in the examples described later. On the other hand, F-510 etc. were inferior. Also from this viewpoint, MegaFuck F-410 and F-444 are particularly preferable, and F-444 is more particularly preferable.

The weight average molecular weight of the surfactant is preferably 30,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and further preferably 4,000 or less. preferable. As a lower limit, it is practical that it is 500 or more.
The molecular weight of the surfactant is the same as that described in Example 1 of JP-A No. 2001-208736, specifically, Asahiklin AK-225 SEC grade 1 is used as the mobile phase, and the polymer is used as the SEC column. Two PL gels 5μm MIXED-E (inner diameter 7.5 mm, length 30 cm) manufactured by Laboratories were connected in series, the mobile phase flow rate was 1.0 ml / min, the column temperature was 37 ° C., and the detector Is measured by a method in which a differential refractive index (RI) detector is used and the polarity is −.

The content of the surfactant is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more in the solid content of the film-forming composition. More preferably it is. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and may be 1% by mass or less, and may be 0.5% by mass. % Or less, 0.1 mass% or less, or 0.01 mass% or less.
It is preferable that it is 0.0001 mass% or more with respect to the whole composition, It is more preferable that it is 0.0005 mass% or more, It is further more preferable that it is 0.001 mass% or more. The upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
The content of the surfactant with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 parts by mass or more. Is more preferable. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and 1 part by mass. Or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.1 parts by mass or less.
Surfactant may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
By adjusting the surfactant to the above range, the surface tension of the coating film of the film-forming composition can be lowered, the formation of Benard cell or its effect can be effectively suppressed, and the surface state of the film can be improved. Therefore, it is preferable.

<< Plasticizer >>
The plasticizer used in the film-forming composition according to the embodiment of the present invention is not particularly defined as to the type thereof, and a known plasticizer can be used.
Specific examples include phthalic acid esters, adipic acid esters, trimellitic acid esters, polyesters, phosphoric acid esters, citric acid esters, epoxy plasticizers, sebacic acid esters, azelaic acid esters, maleic acid esters, and benzoic acid esters. Epoxy plasticizers are preferred.
Examples of the epoxy plasticizer include epoxidized oil (epoxidized soybean oil, epoxidized linseed oil), epoxidized fatty acid alkyl (eg, octyl) ester, and the like.
The epoxy plasticizer preferably has an epoxy group of the following formula e1 or e2 in the molecule.

That is, the one in which the formula e1 is introduced at the end or in the middle of the olefin chain or paraffin chain constituting the plasticizer, the one in which the formula e2 is introduced in the middle of the chain, or both are introduced at both the end and in the middle Can be mentioned. The epoxy plasticizer is preferably a fatty acid or an oil and fat, and more preferably a carboxyl group is introduced into the olefin chain or paraffin chain. However, this carboxyl group may be partially or fully esterified with an alkyl group or the like. The plasticizer preferably has 3 to 48 carbon atoms, more preferably 4 to 36, and still more preferably 6 to 24.
Specific examples include ADEKA Corporation, O-180A, O-130P, D-32, and D-55 (all trade names), and among them, O-180A, O-130P, and D-32 are preferable. .

The plasticizer preferably has a viscosity at 25 ° C. of 40 mPa · s or more, more preferably 100 mPa · s or more, and further preferably 200 mPa · s or more. The upper limit is practically 800 mPa · s or less. The SP value is preferably 8 or more, and more preferably 8.5 or more. There is no particular upper limit, but 9.5 or less is practical.

The content of the plasticizer is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more in the solid content of the film-forming composition. More preferably. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and may be 1% by mass or less, and may be 0.5% by mass. % Or less, 0.1 mass% or less, or 0.01 mass% or less.
The content of the plasticizer with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 parts by mass or more. Further preferred. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and 1 part by mass. Or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.1 parts by mass or less.
Only one kind of plasticizer or two or more kinds of plasticizers may be contained. When 2 or more types are included, the total amount is preferably within the above range.
By setting the plasticizer within the above range, it is preferable to prevent the film surface from being dried, to prevent the Benard cell from continuing, and to obtain a better surface state of the coated film.

<< photopolymerization initiator >>
The film-forming composition may contain a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator.
There is no restriction | limiting in particular as radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators. For example, a radical photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient 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 using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

As the photo radical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Can be mentioned. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, the contents of which are incorporated herein.

Examples of ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

As the photo radical polymerization initiator, an oxime compound is more preferable. By using the oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
As preferable oxime compounds, the description in paragraphs 0080 to 0083 of JP-A-2015-189883 can be referred to, and the contents thereof are incorporated in the present specification.

Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.

Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can be used.

When it contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. More preferably, the content is 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. The photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.

<< Thermal radical polymerization initiator >>
The film forming composition may contain a thermal radical polymerization initiator.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. More preferably, it is 5 to 15% by mass. The thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.

<< polymerizable compound >>
<<< Radically polymerizable compound >>>
The film-forming composition preferably contains a radical polymerizable compound.
As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl group, vinyl group, (meth) acryloyl group, and allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.

The number of radical polymerizable groups contained in the radical polymerizable compound may be one or two or more. However, the radical polymerizable compound preferably has two or more radical polymerizable groups, and preferably has three or more radical polymerizable groups. More preferred. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

From the standpoint of developability, the film-forming composition preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher radical polymerizable compound. More preferably. Further, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher functional radically polymerizable compound. In addition, the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.

Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substituted reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid. As specific examples, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.

The radical polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Many products such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, JP-B-48-0417 Urethane (meth) acrylates as described in JP-A-8, JP-B-50-006034, JP-A-51-037193, JP-A-48-064183, JP-B49-043191 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B-52-030490, and mixtures thereof Can do. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. In addition, polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be exemplified.
Further, as other preferable radical polymerizable compounds other than those described above, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having a carbonic acid or a cardo resin.
Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-024933. And vinyl phosphonic acid compounds. Further, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A No. 2015-034964 can also be preferably used, and the contents thereof are incorporated in the present specification.

Further, compounds described in JP-A-10-062986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a radically polymerizable compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as other radical polymerizable compounds, the contents of which are incorporated herein.

Examples of the radical polymerizable compound include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku ( A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl group via an ethylene glycol residue or a propylene glycol residue A bonded structure is preferred. These oligomer types can also be used.

Examples of commercially available radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60 which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- manufactured by Nippon Kayaku Co., Ltd. 10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306 , AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF Corporation) and the like.

Examples of the radical polymerizable compound include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, and the like. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Further, as radically polymerizable compounds, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphate group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A radically polymerizable compound having a group is more preferable. Particularly preferably, in the radical polymerizable compound in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentayl. A compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.

A monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. Monofunctional radically polymerizable compounds include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) Acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl compounds such as N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Le compounds are preferably used. As the monofunctional radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

<<< Polymerizable compound other than the above-mentioned radical polymerizable compound >>>
The film-forming composition can further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.

(Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

(Wherein t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ¹⁰⁵ represents a group represented by —OR ¹⁰⁶ or —OCO—R ^107. R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

(Wherein R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by —OR ⁴⁰⁶ or —OCO—R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or a carbon atom. An organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

(Wherein u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵⁰⁵ represents a group represented by —OR ⁵⁰⁶ or —OCO—R ^507. R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC Examples include MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diacetylmethyl-p-cresol, and the like. It is done.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing of the composition and suppression of warpage of the film.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade names, and the like (Ltd.) ADEKA). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

(Oxetane compound (compound having oxetanyl group))
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester. As specific examples, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.

(Benzoxazine compound (compound having a benzoxazolyl group))
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.

Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo An oxazine compound is mentioned. These may be used alone or in combination of two or more.

When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the film-forming composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
As the polymerizable compound, one kind may be used alone, or two or more kinds may be mixed and used. When using 2 or more types together, it is preferable that the total amount becomes said range.

<< Migration inhibitor >>
The film forming composition preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the film of the film-forming composition.
The migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Salicylic acid derivative compounds and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A. The compounds described in paragraph 0052 and the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.

Specific examples of the migration inhibitor include the following compounds.

When the film forming composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the film forming composition. More preferably, the content is 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass.
Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.

<< Polymerization inhibitor >>
The film-forming composition preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4 ′. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. In addition, a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of WO2015 / 125469 can also be used.
Moreover, the following compound can be used (Me is a methyl group).

When the film-forming composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the film-forming composition, 0.02 It is more preferably from 3 to 3% by mass, and further preferably from 0.05 to 2.5% by mass.
Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

<Metal adhesion improver>
The film-forming composition preferably contains a metal adhesion improver for improving adhesion with a metal material used for electrodes, wirings, and the like. Examples of metal adhesion improvers include silane coupling agents.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP-A No. 2014-191002, compounds described in paragraphs 0063 to 0071 of WO 2011/080992, and JP-A No. 2014-191252. The compounds described in paragraphs [0060] to [0061], the compounds described in paragraphs [0045] to [0052] of JP-A No. 2014-041264, and the compounds described in paragraph [0055] of WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.

As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0 to 100 parts by mass of the polyimide precursor. The range is from 5 to 5 parts by mass. Adhesion between the film after the curing step and the metal layer is improved by setting the above lower limit value or more, and heat resistance and mechanical properties of the film after the curing step are improved by setting the upper limit value or less. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.

<Curing accelerator>
The film forming composition may contain a curing accelerator. The curing accelerator may be a heat curing accelerator or a photocuring accelerator.
<< Thermosetting accelerator >>
The thermosetting accelerator is preferably one that generates a base by heating. A preferable range of the heating temperature (base generation temperature) is the same as the temperature defined in the heating step described later. Salts of tertiary amines or quaternary ammonium cations and carboxylate anions are preferred. The tertiary amine and quaternary ammonium cation are preferably represented by any of the following formulas (Y1-1) to (Y1-4).

R ^Y1 represents an organic group having an n ^Y value (n ^Y is an integer of 1 to 12), and is preferably a hydrocarbon group. The hydrocarbon group includes an alkane-containing group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), and an alkene group (preferably 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), a group containing an aromatic hydrocarbon (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and further preferably 6 to 10), or a combination thereof. . R ^Y1 is preferably an aromatic hydrocarbon group. R ^Y1 is a substituent T (hydroxyl group, carboxyl group, amino group (NR ^N ₂ ), alkoxyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably) as long as the effects of the present invention are not impaired. 3 is more preferable), an acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an alkoxycarbonyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). Preferably 2 to 3), acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), carbamoyl group (preferably 1 to 12 carbon atoms, 1 to 6 carbon atoms). still more preferably, 1 to 3 is more preferred), R ^N is a group synonymous with the groups represented by hydrogen or R ^Y2.) may have.
R ^Y2 to R ^Y5 each independently represents a hydrogen atom or a hydrocarbon group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), and an alkyl group (having a carbon number of 1 to 36). 36 is preferred, 1 to 24 is more preferred, 1 to 23 is more preferred, an alkenyl group (preferably having 2 to 36 carbon atoms, more preferred is 2 to 24, still more preferred being 2 to 23), and an alkynyl group (having carbon numbers). 1 to 36 are preferred, 1 to 24 are more preferred, 1 to 23 are more preferred, and an aryl group (preferably having 6 to 22 carbon atoms, more preferred is 6 to 18 and even more preferred is 6 to 10).
R ^Y6 represents an alkyl group (preferably having a carbon number of 1 to 36, preferably 2 to 24, more preferably 4 to 18), or an alkenyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, and 4 to 18). Is more preferable), an alkynyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24, more preferably 4 to 18), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). To 10 is more preferable).
n ^Y represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
n ^X represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
In R ^Y2 to R ^Y6 , the alkyl group, alkenyl group, and alkynyl group may be cyclic or chain-like, and in the case of a chain, it may be linear or branched. In the alkyl group, alkenyl group, alkynyl group, and aryl group, a linking group L (carbonyl group, oxygen atom, sulfur atom, NR ^N , alkylene group (carbon number 1 to 12 is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable, an alkenylene group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 are more preferable), an arylene group (carbon number). 6 to 22 is preferable, 6 to 18 is more preferable, and 6 to 10 is more preferable), or a linking group according to a combination thereof may be interposed.
Two or more of R ^Y2 to R ^Y6 may be bonded to each other to form a ring.
R ^Y2 to R ^Y6 may have a substituent T.

R ^Y7 to R ^Y16 are a hydrogen atom or a substituent. However, not all of R ^Y7 to R ^Y9 are hydrogen atoms. The substituent is preferably an organic group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), which may intervene a linking group L and has a substituent T. It is preferably a hydrocarbon group that may be present. As the hydrocarbon group, an R ^Y2 group is preferred.
In the formula (Y1-2), R ^Y7 and R ^Y8 are carboxyalkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms; preferably 1 to 12 carboxyl groups). 1 to 6 are more preferable, and 1 to 3 are more preferable. R ^Y9 is preferably an aromatic group, and is preferably an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10). Alternatively, an alkoxycarbonyl group substituted with an aromatic group is preferred (the alkoxyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and the aromatic group preferably has 6 to 22 carbon atoms). 6 to 18 are more preferable, and 6 to 14 are more preferable.
In another preferred embodiment of the formula (Y1-2), R ^Y7 and R ^Y8 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3). R ^Y9 is preferably an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), and is preferably an alkoxycarbonyl group having an aromatic group.
In the formula (Y1-3), R ^Y11 and R ^Y13 are preferably hydrogen atoms. R ^Y14 and R ^Y15 may be combined with each other to form a substituent of the form ═C (NR ^N ₂ ) ₂ (= means a double bond to a nitrogen atom).
In the formula (Y1-4), R ^Y13 is preferably a hydrogen atom, and R ^Y10 , R ^Y11 , R ^Y12 and R ^Y16 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). ~ 3 are more preferred). At this time, R ^Y11 and R ^Y16 , R ^Y10 and R ^Y12 are preferably bonded to form a ring to form a bicyclo compound. Specific examples include diazabicyclononene and diazabicycloundecene.

In this embodiment, the carboxylic acid anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is represented by the following formula (X1). It is preferable.

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

In the present embodiment, the electron-withdrawing group means a group in which Hammett's substituent constant σm exhibits a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
Examples of substituents in which σm has 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 (σm = 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 (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

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

In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3). More preferably), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 6 carbon atoms). 10 is more preferable), and represents a hydroxyl group or a carboxyl group. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). When R ^x1 to R ^x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed. These alkyl group, alkenyl group, aryl group, and Ar may have a substituent T as long as the effects of the present invention are not impaired. Among these, Ar preferably has a carboxyl group (preferably 1 to 3). * Represents a bonding position.
L ¹ is a group having the same meaning as the linking group L, and is preferably —CR ^X2 R ^X3 —, —Ar ¹ —, or a combination thereof. Ar ¹ is an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).
Np represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.

The molecular weight of the thermosetting accelerator is preferably 100 or more and less than 2000, and more preferably 200 to 1000.
Specific examples of the thermosetting accelerator include an acidic compound that generates a base when heated to 40 ° C. or higher described in International Publication No. 2015/199219 and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0 to 4, These contents are incorporated herein.

When the thermosetting accelerator is used, the content of the thermosetting accelerator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, and further preferably 5% by mass or less.
1 type (s) or 2 or more types can be used for a thermosetting accelerator. When using 2 or more types, it is preferable that a total amount is the said range. Moreover, the composition for film formation can also be set as the structure which does not contain a thermosetting accelerator substantially. “Substantially free” means less than 0.01% by mass, more preferably less than 0.005% by mass, based on the total solid content of the composition.

<< Photocuring accelerator >>
The film forming composition may contain a photocuring accelerator. The photocuring accelerator is preferably one that generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, the base (base It is preferable that the substance generate | occur | produces an active substance). Since the base generated by exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used. The preferable conditions for exposure are the same as those defined in the exposure step described later.
A well-known thing can be used as a photocuring accelerator. For example, the base component was neutralized by forming a salt, such as a transition metal compound complex, a compound having an ammonium salt structure, or an amidine moiety made latent by forming a salt with a carboxylic acid. Examples include ionic compounds, and nonionic compounds in which a base component is made latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.

Examples of the photocuring accelerator include a photocuring accelerator having a cinnamic amide structure as disclosed in JP2009-080452A and International Publication No. 2009/123122, JP2006-189591A and A photocuring accelerator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure and a carbamoyloxime structure as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581 Although a photocuring accelerator etc. are mentioned, it is not limited to these, In addition, the structure of a well-known photocuring accelerator can be used.

Other examples of the photocuring accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205A, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.

Commercially available photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.

When the photocuring accelerator is used, the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the 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% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a photocuring accelerator. When using 2 or more types, it is preferable that a total amount is the said range.

<Other additives>
The film-forming composition is within a range that does not impair the effects of the present invention, and various additives, for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants other than those described above, A higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<< thermal acid generator >>
The film forming composition may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A. The preferable range of the heating temperature (acid generation temperature) of the thermal acid generator is the same as the temperature defined in the heating step described later.

0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 parts by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less from the viewpoint of electrical insulation of the film.
One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Sensitizing dye >>
The film-forming composition may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a thermosetting accelerator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.

When the film-forming composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass with respect to the total solid content of the film-forming composition, preferably 0.1 to The content is more preferably 15% by mass, and further preferably 0.5 to 10% by mass. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<< Chain transfer agent >>
The film forming composition may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

When the film-forming composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the film-forming composition, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.

<< Higher fatty acid derivative >>
In order to prevent polymerization inhibition due to oxygen, the film-forming composition is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the process of drying after coating. May be.
When the film-forming composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the film-forming composition. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<Restrictions on other contained substances>
The water content of the film-forming composition is preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.6% by weight from the viewpoint of the coating surface properties.

The metal content of the film-forming composition is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and even more preferably less than 0.5 ppm by weight 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, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities that are unintentionally contained in the film-forming composition, the raw material having a low metal content is selected as the raw material constituting the film-forming composition. For example, the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.

The film-forming composition preferably has a halogen atom content of less than 500 ppm by weight, more preferably less than 300 ppm by weight, and even more preferably less than 200 ppm by weight from the viewpoint of wiring corrosivity. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.

As the container for the film forming composition, a conventionally known container can be used. In addition, as a container, for the purpose of suppressing contamination of raw materials and compositions, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.

<Preparation of composition>
The film-forming composition can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore sizes or materials may be used in combination. Various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and filter. When the pressure is applied for filtration, the pressure applied 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 an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Each process>
The production method of the present invention preferably includes an exposure step of exposing after the film formation step and a development step of developing the exposed film. After this development, the exposed film can be further cured by heating.

Further, to form a laminate, after forming the film according to the above-described film manufacturing method, the film forming process and heating process, the film forming process, the exposure process, and the developing process (further heating process if necessary) ) Are preferably performed in the above order. In particular, it is preferable to perform each of the above steps a plurality of times in order (preferably 2 to 5 times, that is, 3 to 6 times in total). By laminating the films in this way, it is possible to obtain a laminated body that is laminated a desired number of times. In forming a laminate, it is also preferable to apply a metal layer.

<< Film formation process >>
As described above, the production method of the present invention preferably includes a film forming step in which the film forming composition is applied to a substrate to form a film.
The type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. However, in the present invention, the substrate is a member including at least a metal (for example, a substrate provided with a metal layer). In the present invention, by applying the film-forming composition to the metal surface by slit coating, the surface shape of the resin film described above can be improved. Further, the shape of the substrate is preferably a quadrangle, and more preferably a rectangle.

In the film production method of the present invention, it is preferable to use a slit coater as means for applying the film-forming composition to the substrate.
The slit width of the nozzle is preferably 20 μm or more, more preferably 50 μm or more, and further preferably 80 μm or more. As an upper limit, it is preferable that it is 250 micrometers or less, It is more preferable that it is 200 micrometers or less, It is further more preferable that it is 150 micrometers or less.
The slit gap is preferably 30 μm or more, more preferably 50 μm or more, and further preferably 70 μm or more. As an upper limit, it is preferable that it is 200 micrometers or less, It is more preferable that it is 150 micrometers or less, It is further more preferable that it is 120 micrometers or less.
The scanning speed may be 1 mm / s or more, preferably 10 mm / s or more, more preferably 20 mm / s or more, and further preferably 30 mm / s or more. As an upper limit, it is preferable that it is 500 mm / s or less, It is more preferable that it is 400 mm / s or less, It is further more preferable that it is 300 mm / s or less.
The coating film thickness is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more. As an upper limit, it is preferable that it is 100 micrometers or less, It is more preferable that it is 80 micrometers or less, It is further more preferable that it is 50 micrometers or less.

<< Drying process >>
In the manufacturing method of this invention, after forming a film | membrane, the process of drying in order to remove a solvent may be included. A preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
The film thickness of the dried film can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less. This thickness is the same in the film thickness after the heating step described later.

<< Exposure process >>
For example, the exposure dose in the exposure step is preferably 100 to 10,000 mJ / cm ² , more preferably 200 to 8000 mJ / cm ^{2 in} terms of exposure energy at a wavelength of 365 nm.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and is preferably 240 to 550 nm.
The exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h. Line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and the like. For the film-forming composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and i-line exposure is particularly preferable. Thereby, particularly high exposure sensitivity can be obtained.

<< Development process >>
The development method in the development step is not particularly limited as long as a desired pattern can be formed, and for example, development methods such as paddle, spray, immersion, and ultrasonic waves can be adopted.
Development is preferably performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropyl) Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Cyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. A preferred example of the sulfoxide is dimethyl sulfoxide.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developer is preferably 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of an organic solvent. Further, 100% by mass of the developer may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly defined, but it can usually be carried out at 20 to 40 ° C.
After treatment with a developer, rinsing may be further performed. The rinsing is preferably performed with a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the film-forming composition. The rinse time is preferably 5 seconds to 1 minute.

<< Heating process >>
In the heating step, the cyclization reaction of the polyimide precursor proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 500 ° C, more preferably 80 to 450 ° C, still more preferably 140 to 400 ° C, and still more preferably 160 to 350 ° C.
Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature increase rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of the amine while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, the film remains. Stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the film-forming composition is applied onto a substrate and then dried, the temperature after this drying is performed, for example, a temperature 30 to 200 ° C. lower than the boiling point of the solvent contained in the film-forming composition. It is preferable that the temperature is gradually raised.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the film. Although the reason is not certain, it is considered that the ethynyl group of the polyimide precursor between layers proceeds with a crosslinking reaction at this temperature.

Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. You may perform the pre-processing process of these. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<< Metal layer formation process >>
You may apply and form a metal layer on the surface of the film | membrane of the film forming composition after image development processing.
There are no particular limitations on the metal layer, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest part.

<< Lamination process >>
The laminating step may include performing the film forming step and the heating step, or the film forming step, the exposure step, and the developing step in the above order again on the surface of the film or metal layer of the film forming composition. Good. The laminating step may further include the drying step and the heating step.
When a lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process. An example of the surface activation treatment is plasma treatment.
The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers.
That is, after the metal layer is provided, the film forming step and the heating step of the film forming composition, or the film forming composition, the exposure step is performed so as to cover the metal layer. It is preferable to carry out the steps and the above-described development step (further heating step if necessary) in the above order. By alternately performing the laminating step of laminating the film (resin) of the film forming composition and the metal film forming step, the film (resin layer) and the metal layer of the film forming composition can be alternately laminated. .

Specific examples of the semiconductor device in which the film of the film forming composition obtained by the production method of the present invention is used for forming the interlayer insulating film for the rewiring layer are described in paragraphs 0213 to 0218 of JP-A-2016-027357. And the description of FIG. 1 can be referred to, the contents of which are incorporated herein.

The present invention also discloses a method for manufacturing a semiconductor device in which a chip is arranged on the film of the present invention. Furthermore, the manufacturing method of the semiconductor device which arrange | positions a chip | tip to the laminated body of this invention is disclosed. Regarding the chip and the chip arrangement method here, the description of the semiconductor three-dimensional mounting technology, Junichi Hamada, CQ Publisher, issued on June 1, 2011 can be referred to, and the contents thereof are incorporated in this specification. .

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. “Parts” and “%” are based on mass unless otherwise specified.

<Synthesis Example 1>
[Synthesis of polyimide precursor resin A-1 from pyromellitic dianhydride, 4,4′-diaminodiphenyl ether and 3-hydroxybenzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were mixed with 50 mL of N-methylpyrrolidone. And dried with molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A few minutes after heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 mL N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of thionyl chloride was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. The viscosity increased during the addition of thionyl chloride. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had Mw = 22800 and Mn = 8100.

<Synthesis Example 2>
[Synthesis of polyimide precursor resin A-2 from oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a stirrer, condenser and internal thermometer. . 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. Next, after the mixture was cooled to −20 ° C., 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to give a clear solution. Next, a solution obtained by dissolving 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. The viscosity increased during the addition of 4,4'-diaminodiphenyl ether. Subsequently, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 500 rpm. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had Mw = 23500 and Mn = 8800.

<Synthesis Example 3>
[Synthesis of polyimide precursor resin A-3 from oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
While removing moisture in a dry reactor equipped with a flat bottom joint fitted with a stirrer, condenser and internal thermometer, 10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 3,3 ′, 4,4 9.47 g (32.3 mmol) of '-biphenyltetracarboxylic dianhydride was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. Next, after the mixture was cooled to −20 ° C., 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to give a clear solution. Next, 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. The viscosity increased during the addition of 4,4'-diaminodiphenyl ether. Subsequently, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 500 rpm. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had Mw = 24300 and Mn = 9500.

<Preparation of film-forming composition>
The composition for film formation of each Example and a comparative example was prepared as a uniform solution by mix | blending in the ratio (mass part) shown in the following table. In the examples described later, the obtained composition was used after being filtered using a polyethylene filter having a pore size of 0.8 μm.

<Film formation by slit coating>
As a substrate, a substrate was prepared by forming a copper film having a thickness of 100 nm on the surface of a non-alkali glass substrate having a width of 150 mm, a length of 150 mm, and a thickness of 0.7 mm by sputtering. Using the slit coater (LC-R300G, manufactured by SCREEN Finetech Solutions Co., Ltd., where the slit head width is set to 100 mm and the coating length is set to 100 mm) on the surface of this substrate, the coating film of the film forming composition prepared above is used. Formed. The detailed conditions of the slit coater apparatus are as shown in the table below. This was left to stand at 23 ° C. and a reduced pressure of 50 Pa for 5 minutes, and then dried on the hot plate at 100 ° C. for 5 minutes. The coating film thickness (after drying) was measured every 10 mm from the position of 10 mm from the end of the coating part using the F20 film thickness measurement system manufactured by Filmetrics, and the average value was taken. At the time of film formation, the nozzle head was immersed in the immersion liquid in the head standby step under the conditions shown in the following table. Further, after the film formation, the nozzle head was immersed in the cleaning liquid in the head cleaning process. The temperature during immersion and washing was (normal temperature (23 ° C.)).

<Applicability>
The applicability during the slit coating was evaluated. The coating film formed on the substrate is left to stand at 23 ° C. and a reduced pressure of 50 Pa for 5 minutes, and then dried under the condition of standing at a hot plate at 100 ° C. for 5 minutes. confirmed. The observation area was the entire surface excluding 10 mm from the end face of the application part. In each example and comparative example, an average value of three samples was adopted.
There was little or no repelling or streaking, and it was uniform: Excellent Repelling and streaking were slightly recognized, but it was almost uniform: Good Repelling and streaking were many: Substandard

<Surface shape after coating and drying>
The surface condition after coating and drying during the slit coating was evaluated. The coating film (after drying) formed on the substrate was visually observed, and the surface shape was confirmed from the reflection state of the fluorescent lamp. In each example and comparative example, an average value of three samples was adopted.
Fluorescent lamps appear to be mirror-reflected as they are throughout the application area-Gloss: Excellent. At least part of the application area appears to cause the fluorescent lamp to appear blurred.-Weak skin: Good. Fluorescent lamp appears to be blurred throughout the application area. Yuzu skin: below standard

<In-plane uniformity after coating and drying>
The in-plane uniformity of the film thickness after coating and drying during the slit coating was evaluated. The film thickness distribution of the coating film on the surface of the substrate provided with the coating film (after drying) is 90 mm in length and 10 mm in width excluding the coating part end 10 mm by a film thickness measuring device (F20 film thickness measurement system manufactured by Filmetrics). The 90 mm region was measured at 81 points every 10 mm, and the maximum and minimum difference was defined as TTV (Total thickness variation). In each example and comparative example, an average value of three samples was adopted.
TTV was measured in an area excluding 10 mm from the end of the coating part.
≦ 1 μm: Excellent> 1 μm, ≦ 2 μm: Good> 2 μm: Below standard

<Drying time after application>
In the above drying process, the time from drying on the hot plate to drying was evaluated. When the surface of the coated part was touched with a cotton swab after the specified time had elapsed, if a trace remained, drying was incomplete, and if no trace remained, drying was completed. In each example and comparative example, an average value of three samples was adopted. In addition, the measurement was made into the drying time at 100 degreeC.
≦ 300 sec: excellent> 300 sec, ≦ 400: good> 400 sec: below standard

<Nozzle head dirt after nozzle head cleaning>
In the above film forming process, the cleaning liquid having the composition shown in the table is put into a vat, and the nozzle head is immersed at 23 ° C. for the time shown in the table so that the slit of the nozzle head is immersed in the cleaning liquid. The dirt on the head was evaluated. Each example and comparative example was adopted in three tests. In addition, the measurement was made into the drying time at 100 degreeC.
Dirt was not confirmed in all three times: None Dirt was confirmed more than once in 3 times: Existence

<Member adhesion of coating film (shear test)>
Shear tests were performed on the coating films after drying the films formed by slit coating on the various substrates described in Tables 1 to 9. The measuring device (XYZTEC Co., Ltd. Condor Sigma bond tester) was used. In the test, a film dried after coating on the substrate was exposed with an exposure amount of 400 mJ / cm ² using a negative photomask capable of irradiating a 100 μm square pattern, and after 30 minutes, the exposed film was developed with cyclopentanone. After that, a 100 μm square film was formed by rinsing with PGMEA, and the film was pressed at 10 μm / s from the side (with a needle set at a position of 5 μm from the ground). In each example and comparative example, an average value of three samples was adopted.
<10 g: below standard ≧ 10 g, <40 g: good ≧ 40 g: excellent The same shear test was performed on a Cu-plated substrate, an Al—Si—Cu alloy-plated substrate, a Ti sputter substrate, and a Ni sputter substrate with a coating film. . Further, in Examples 32 to 36, the same shear test was performed on the Si substrate provided with the coating film. The evaluation criteria are the same.

<Moisture resistance>
Further, a PCT (pressure cooker test) was performed on the Cu plated substrate and the Ti sputter substrate with the coating film. A PCT test apparatus (EHS-412M, manufactured by Espec Corp.) was used. The treatment conditions for the coating film were 121 ° C., 100% relative humidity (RH), and 500 hours. About the coating film after a process, adhesive evaluation (shear test) was performed on the same conditions as the above-mentioned test of <the member adhesiveness of a coating film>. The evaluation criteria are the same.

sec: second, min: minute * 1 Immersion: Immersion during head standby: 30 seconds after application, 30 seconds after application * 2 Comparative example 2: * Dissolving failure that cannot be dried by absorbing moisture in the air when DMSO is 100% : Cannot be applied because the solid content could not be dissolved in the solvent. Cannot be measured.

Solubility (% by mass) of polyimide precursors A-1, A-2 and A-3 in each solvent [23 ° C.]

Surfactant (Megafuck [trade name], DIC)
For water solubility, the amount (g) dissolved in 100 g of water at 23 ° C. was shown in units of mass%. The molecular weight is a weight average molecular weight.

(C) Photoradical polymerization initiator C-1: IRGACURE OXE-01 manufactured by BASF
C-2: The following compound

(D) Radical polymerizable compound D-1: manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-9300
D-2: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer)

(E) Polymerization inhibitor E-1: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-2: 4-methoxyphenol
(F) Migration inhibitor (rust inhibitor)
F-2: 1H-tetrazole

(G) Metal adhesion improver (silane coupling agent)
G-1: manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-602
G-2: The following compound (wherein Et represents an ethyl group)

(H) Curing accelerator (thermal base generator)
H-1: The following compound

H-2: The following compound

As the plasticizer, O-180A, O-130P and D-32 (all manufactured by ADEKA) were used as shown in each table.

As can be seen from the above results, in the present invention, when carrying out slit coating, as a film-forming composition to be applied, a composition containing a polyimide precursor, a specific solvent and a surfactant or a plasticizer is applied. Even when a coating film was formed on the metal surface, a good surface state of the coating film was obtained. Further, in a preferred embodiment of the present invention, the coating property of the film-forming composition, the in-plane uniformity after coating and drying, the drying time after coating, the nozzle head contamination after cleaning the nozzle head, and the member adhesion of the coating film Good performance was obtained.

<Example of exposure and development>
The film forming composition prepared in Example 1 was applied on a copper wafer (corresponding to a metal layer or a member containing metal) by slit coating to form a coating film. The obtained coating film was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform precured film (film of a film forming composition) having a thickness of about 15 μm. This was exposed using an aligner (Karl-Suss MA150 [trade name]) through a mask having a line-and-space pattern (step: 5 to 20 μm). Exposure was performed with a high-pressure mercury lamp, and irradiation was performed at 500 mJ / cm ^{2 in} terms of exposure energy at a wavelength of 365 nm.
The precured film after the exposure was dissolved in cyclopentanone for 75 seconds and developed with a paddle. The line width of the developed part was evaluated according to the following criteria. The exposed width of the underlying substrate after development was within ± 10% of the mask size, and it was confirmed that good exposure and development were possible.
The formed resin pattern was heated at 250 ° C. for 3 hours to advance the cyclization reaction of the polyimide precursor to obtain a polyimide resin, thereby obtaining an extremely stable and strong resin pattern while being a fine pattern. .
Since the produced resin pattern is made of polyimide, it has excellent insulating properties, has good compatibility with metals as described above, and can suitably cope with fine processing. Therefore, WL-CSP ( It has been found to be particularly suitable for the production of rewiring layers of wafer level chip size packages).

In Example 1, the polyimide precursor A-1 was changed to the polyimide precursor A-2 or A-3, and the others were performed in the same manner. The same excellent effect as in Example 1 was obtained. On the other hand, in Comparative Example 1, the polyimide precursor A-1 was changed to the polyimide precursor A-2 or A-3, and the others were performed in the same manner. Similar to Comparative Example 1, the surface condition after coating and drying was inferior.

21 Nozzle head 22 Nozzle head cleaner 23 Conveying section 21a Resin 24 Roller 25 Roller butt 25b Liquid cutting blade 25a Cleaning liquid 26 Maintenance section 100 Slit coating device

Claims

A polyimide precursor;
At least two solvents having different solubility at 23 ° C. in the polyimide precursor;
Using a composition comprising at least one selected from the group consisting of a surfactant and a plasticizer,
A method for producing a film, comprising the step of performing slit coating on a member, wherein the member contains a metal at least in part.
The method for producing a film according to claim 1, wherein the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
The method for producing a film according to claim 1 or 2, comprising a head cleaning step of cleaning the nozzle head with a cleaning liquid after the slit coating step.
The slit coating step includes a head standby step, and the nozzle head is immersed in an immersion liquid in the head standby step, and the immersion liquid is a liquid having a composition that is 90% by mass or more in common with the cleaning liquid. The method for producing a film according to claim 3.
The method for producing a film according to claim 3 or 4, wherein the cleaning liquid contains a solvent having the highest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
The method for producing a film according to any one of claims 3 to 5, wherein the cleaning liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
The method for producing a film according to claim 4, wherein the immersion liquid contains a solvent having the highest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
The method for producing a film according to claim 4 or 7, wherein the immersion liquid contains a solvent having the lowest solubility of the polyimide precursor at 23 ° C among the at least two kinds of solvents.
The method for producing a film according to any one of claims 1 to 8, comprising an exposure step of exposing the film formed by the slit coating and a development step of developing the exposed film.
The method for producing a film according to any one of claims 1 to 9, further comprising a heating step of heating the film.
A method for producing a laminate, wherein the method for producing a film according to any one of claims 1 to 10 is performed a plurality of times.
The manufacturing method of the laminated body of Claim 11 including the process of applying a metal layer to the said film | membrane.
A method for manufacturing a semiconductor device, wherein a chip is arranged on a film manufactured by the method according to any one of claims 1 to 10.
A method for manufacturing a semiconductor device, in which a chip is arranged on a laminate manufactured by the method according to claim 11.
A film-forming composition used in the production method according to any one of claims 1 to 10, comprising a polyimide precursor and at least two solvents having different solubility at 23 ° C in the polyimide precursor. And a film-forming composition comprising at least one selected from the group consisting of a surfactant and a plasticizer.
The film forming composition according to claim 15, wherein the polyimide precursor is a condensate of dicarboxylic acid or a dicarboxylic acid derivative and a diamine.
Of the at least two solvents, the solvent having the highest solubility of the polyimide precursor is a sulfoxide solvent, and of the at least two solvents, the solvent having the lowest solubility of the polyimide precursor is a ketone or The composition for film formation according to claim 15 or 16, which is a solvent for lactones.
Of the at least two solvents, the total mass of the solvent having a solubility of the polyimide precursor higher than the average value below, and of the at least two solvents, the solubility of the polyimide precursor is lower than the average value below. The film-forming composition according to any one of claims 15 to 17, wherein the ratio of the total mass is 10:90 to 45:55;
The average value is an average value of the solubility of the solvent having the highest solubility of the polyimide precursor at 23 ° C. and the solubility of the polyimide precursor having the lowest solubility at 23 ° C.
The film forming composition according to any one of claims 15 to 18, wherein the surfactant contains a fluorine atom.
The film-forming composition according to claim 19, wherein the surfactant is a compound containing a perfluoroalkyl group and having a weight average molecular weight of 5,000 or less and is soluble in water.
The film-forming composition according to any one of claims 15 to 20, wherein the content of the surfactant is 0.005 to 2% by mass in the solid content.
The film-forming composition according to any one of claims 15 to 21, wherein the plasticizer is an epoxidized oil.
The film-forming composition according to any one of claims 15 to 22, wherein the content of the plasticizer is 0.005 to 2% by mass in the solid content.