JPWO2019163860A1 - A film manufacturing method, a laminate manufacturing method, a semiconductor device manufacturing method, and a film forming composition. - Google Patents

Abstract

A composition comprising a polyimide precursor, at least two solvents having different solubilities in the polyimide precursor at 23 ° C., and at least one selected from the group consisting of surfactants and plasticizers is used on the member. A method for producing a film, comprising a step of performing slit coating, wherein the member contains at least a part of a metal. Furthermore, the present invention relates to a method for producing a laminate, a method for producing a semiconductor device, and a composition for forming a film, which are related to the method for producing this film.

Description

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

Polyimide resin is applied to various applications because it has excellent heat resistance and insulating property. The application is not particularly limited, and examples of semiconductor devices for mounting include the use as a material for an insulating film or a sealing material, or a protective film thereof. It is also used as a base film and coverlay for flexible substrates.
The above-mentioned polyimide resin generally has low solubility in a solvent. Therefore, a method of dissolving the polyimide precursor in a solvent before cyclization is often used. As a result, excellent handleability can be realized, and when each product as described above is manufactured, it can be applied to a substrate or the like in various forms and processed. The polyimide precursor can then be heated to form a cured product. In addition to the high performance of polyimide resin, from the viewpoint of excellent manufacturing adaptability, its industrial application development is expected more and more.

On the other hand, Patent Document 1 describes that a resin composition containing a surfactant is slit-coated.

Japanese Unexamined Patent Publication No. 2013-243121

Here, as described in Patent Document 1, a technique is known in which a composition containing a polyimide precursor is formed into a film by slit coating (slit coating). However, it has been found that when the slit-coated object 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 problems, and even when a coating film is formed on a metal surface, it is possible to suppress the occurrence of "yuzu skin" and achieve a good surface shape. An object of the present invention is to provide a film manufacturing method using a possible slit coat, a laminate manufacturing method, a semiconductor device manufacturing method, and a film forming composition suitable for use in these manufacturing methods.

As a result of the study by the present inventor based on the above problems, when the composition containing the polyimide precursor is applied in layers by the slit coating method, Benard cells are generated during drying and the surface becomes skin-like. I found it. Then, in the composition containing the polyimide precursor (coating solution for film formation), at least two kinds of solvents having different solubilities at 23 ° C. with respect to the polyimide precursor are used as the solvent, and the above composition contains a surfactant and It has been found that the above-mentioned problems can be solved by blending at least one selected from the group consisting of plasticizers.
Specifically, the above-mentioned problems were solved by the following means <1>, preferably by <2> to <23>.

<1> Using a composition containing a polyimide precursor, at least two solvents having different solubilities in the polyimide precursor at 23 ° C., and at least one selected from the group consisting of a surfactant and a plasticizer. A method for producing a film, which comprises a step of applying a slit coat on a member, wherein the member contains at least a part of a metal.
<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>, which comprises a head cleaning step of cleaning the nozzle head with a cleaning liquid after the step of performing slit coating.
<4> In the step of performing the slit coating, the head standby step is included, the nozzle head is immersed in the immersion liquid in the head standby step, and the immersion liquid has a composition common to the cleaning liquid in an amount of 90% by mass or more. The method for producing a film according to <3>, which is the liquid of.
<5> The method for producing a film according to <3> or <4>, wherein the cleaning liquid contains the solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents.
<6> Production of the film according to any one of <3> to <5>, wherein the cleaning liquid contains the solvent having the lowest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents. Method.
<7> The method for producing a film according to <4>, wherein the immersion liquid contains the solvent having the highest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents.
<8> The method for producing a film according to <4> or <7>, wherein the immersion liquid contains the solvent having the lowest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents.
<9> The method for producing a film according to any one of <1> to <8>, which comprises an exposure step of exposing the film formed by the slit coating and a developing step of developing the exposed film.
<10> The method for producing a film according to any one of <1> to <9>, which further comprises 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>, which comprises a step of applying a metal layer to the film.
<13> A method for manufacturing a semiconductor device in which a chip is placed on a film manufactured by the method according to any one of <1> to <10>.
<14> A method for manufacturing a semiconductor device in which chips are arranged on a laminate manufactured by the method according to <11> or <12>.
<15> A composition for forming a film used in the production method according to any one of <1> to <10>, wherein the solubility of the polyimide precursor and the polyimide precursor at 23 ° C. is different at least. A film-forming composition containing two solvents and at least one selected from the group consisting of surfactants and plasticizers.
<16> The film-forming composition according to <15>, wherein the polyimide precursor is a condensate of a dicarboxylic acid and a diamino compound.
<17> Of the at least two kinds of solvents, the solvent having the highest solubility of the polyimide precursor is a solvent of sulfoxides or lactams, and among the at least two kinds of solvents, the solvent having the highest solubility of the polyimide precursor. The film-forming composition according to <15> or <16>, wherein the low solvent is a solvent for ketones or lactones.
<18> The total mass of the solvent in which the solubility of the polyimide precursor is higher than the following average value among the at least two kinds of solvents, and the solubility of the polyimide precursor in the above two kinds of solvents is higher than the following average value. 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 above-mentioned average value is an average value of the solubility of the solvent having the highest solubility at 23 ° C. of the polyimide precursor and the solubility of the solvent having the lowest solubility at 23 ° C. of the polyimide precursor.
<19> The film-forming composition according to 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 containing 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 a metal surface in a slit coat, it is possible to suppress the occurrence of "yuzu skin" and achieve a good surface shape.

It is a process explanatory drawing (1) for demonstrating the preferable embodiment of the slit coating applied in this invention with a schematic side view. It is a process explanatory drawing (2) for demonstrating the preferable embodiment of the slit coating applied in this invention with a schematic side view. FIG. 3 is a process explanatory view (3) for explaining a preferred embodiment of the slit coat applied in the present invention with a schematic side view.

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having 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 the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, examples of the light used for exposure generally include an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacryloyl", or either.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if 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-equivalent values according to gel permeation chromatography (GPC) measurement unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using any one or more of Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluate shall be measured using THF (tetrahydrofuran). Further, unless otherwise specified, a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection.
The shape, dimensions, number, arrangement location, etc. illustrated 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 solubilities in the polyimide precursor at 23 ° C., and at least one selected from the group consisting of a surfactant and a plasticizer. It is characterized by including a step of performing slit coating on a member containing at least a part of metal by 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 formed into a coating film and then heated and cured. That is, it was presumed that the coating film was a fluid liquid at the stage of application, and as a result, citron skin was formed. As a result, it was speculated that it is important to consider the following points in order to suppress citron skin.
(1) In order to suppress convection at an early stage during drying, a solvent with low solubility is used in addition to a solvent with high solubility, and
(2) Adopt a surfactant to reduce the surface tension of the coating film, or (3) Add a plasticizer to prevent the surface from drying first and continuing internal convection, and as described above. By using two or more solvents having different solubilities and at least one selected from the group consisting of surfactants and plasticizers, it was possible to suppress the skin and succeed in improving the surface condition. .. Furthermore, it has succeeded in improving the adhesion between the polyimide resin layer and the metal (for example, the metal layer). In particular, by using a predetermined surfactant, we have succeeded in obtaining excellent adhesion to copper (for example, a copper layer).
Hereinafter, the present invention will be described in detail.

<Slit coat>
FIG. 1 is a process explanatory view (1) for explaining a preferred embodiment of the slit coat applied in the present invention with a schematic side view. The coating device 100 of the present embodiment includes a transport unit 23 that transports the substrate 30 and a support stage (not shown) that supports the substrate from below. The resist (resin) 21a is discharged from the nozzle head 21 to the substrate 30 through a slit-shaped nozzle, and the substrate 30 is conveyed in the direction of d3 (slit coating step). The transport unit 23 can be composed of a plurality of transport rollers and a transport roller drive unit that rotates them. The nozzle head 21 can be moved up and down in the vertical direction at the timing when the transport unit conveys the substrate 30. Similarly, the support stage (not shown) can also be moved and retracted from directly below the nozzle head. At this time, the nozzle head can be made to stand by and wait for the next substrate to be sent (head standby step). The following nozzle head immersion treatment (immersion treatment step) and cleaning treatment (head cleaning step) may be performed in the head standby step during the slit coating step or after the slit coating step.

In the device 100 of the present embodiment, the nozzle head cleaner 22 is arranged directly below the nozzle head. When the ejection of the resin to the substrate is completed, the nozzle head is lowered (d1) perpendicularly 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 longer, more preferably 0.2 minutes or longer, and even more preferably 0.5 minutes or longer. The upper limit is preferably 10 minutes or less, more preferably 8 minutes or less, and even more preferably 5 minutes or less. As a result, the tip of the nozzle head 21 can be cleaned.

FIG. 3 is a side view of an apparatus for explaining a head maintenance process different from those of FIGS. 1 and 2, and shows an aspect of maintenance (cleaning) of the nozzle head. The device of this embodiment includes a roller 24 that rotates in the d2 direction. The roller vat 25 is filled with the cleaning liquid 25a so that the lower portion of the roller 24 is immersed. The device 100 of the present embodiment is further provided with a drain blade 25b. The roller 24 and the roller butt 25 form a maintenance unit 26. This maintenance unit can be raised and lowered in a direction perpendicular to the substrate surface. By providing such a maintenance unit, the apparatus of the present embodiment can maintain (clean) the nozzle head 21 by raising the maintenance unit 26 without lowering the nozzle head 21 d5 in the maintenance process. It is possible to execute. In the maintenance unit, the liquid flowing from d5 is switched to the cleaning liquid. The time for flowing the cleaning liquid through the nozzle head is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and even more preferably 5 minutes or longer. The upper limit is preferably 120 minutes or less, more preferably 60 minutes or less, and even more preferably 30 minutes or less. As a result, the nozzle head 21 can be cleaned.

In the present invention, as described above, it is preferable to include a head standby step in the step of performing slit coating. In the head standby step, it is preferable that the head is immersed in the immersion liquid. The immersion liquid preferably has a composition common to that of the cleaning liquid in an amount of 90% by mass or more, more preferably a liquid having a composition common to 95% by mass or more, and further preferably having the same composition.
The dipping solution and the cleaning solution each have a composition in which 90% by mass or more is common to the solvent in the film-forming composition, and 95% by mass or more is common in terms of the type and mixing ratio of the compounds. It is more preferably a liquid, and even more preferably the same composition.
The cleaning liquid also preferably contains the 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. Further, the cleaning liquid preferably contains the solvent having the lowest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents contained in the film-forming composition. Further, among at least two kinds of solvents contained in the film-forming composition, it is possible to contain 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 also preferably contains the 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. Further, the immersion liquid preferably contains the solvent having the lowest solubility of the polyimide precursor at 23 ° C. among at least two kinds of solvents contained in the film-forming composition. Further, among at least two kinds of solvents contained in the film-forming composition, it is possible to contain 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.

For the slit coat and the device applicable thereto, Japanese Patent Application Laid-Open No. 2009-070773 can be referred to, and the matters described therein are incorporated in the present specification.

<Composition for film formation>
<< Polyimide precursor >>
The polyimide precursor preferably contains a repeating structural unit (constituent unit) represented by the following formula (1).
A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are independent of each other. Represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² are independently oxygen atoms or NH, and an oxygen atom is preferable.

<<< 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 an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, which have 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. Preferably, an aromatic group having 6 to 20 carbon atoms is more preferable.
R ¹¹¹ is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, the diamine is derived from a linear 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. It is preferably a diamine containing an aromatic group having 6 to 20 carbon atoms, and more preferably a diamine containing an aromatic group. Examples of aromatic groups include:

In the formula, A represents a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O -, - CO -, - S -, - SO 2 -, - It is preferably a group selected from NHCO- and a combination thereof, and is a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-. And more preferably a group selected from -SO _2- , -CH _2- , -O-, -S-, -SO _2- , -C (CF ₃ ) _2- , and -C (CH). ₃ ) It is more preferable that it is a divalent group selected from the group consisting of ₂ −.

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'-diaminodiphenylsulfone , 4,4'-and 3,3'-diaminodiphenylsulfide, 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) hexa Fluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone , 4,4'-Diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ] Sulfur, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl- 4,4'-Diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino Octafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-) Aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone , 3,3-Dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) 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-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7- Diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-Aminophenyl) Hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) ) Tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexa Fluoropropane, 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, Included are at least one diamine selected from 6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

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

Further, a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine, etc., but are limited to these. Not done.
Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® 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 independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L ⁰ is the group of A above. It is synonymous and the preferred range is the same. Ar ⁰ is preferably a phenylene group.

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

R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R ^{50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or It is a trifluoromethyl group.
As a monovalent organic group of R ^{50 to} R ⁵⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkylated group.

R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

<<< R ¹¹⁵ >>>
R ¹¹⁵ in the 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 is synonymous with A and has the same preferred range.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types 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 the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dihydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid 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) propanedian Anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,54-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-phenanthenetetracarboxylic dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

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

<<< R ¹¹³ and R ¹¹⁴ >>>
R ¹¹³ and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is 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, and a group represented by the following formula (III).

In formula (III), ^R200 represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In the formula (III), R ²⁰¹ is 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). ~ 12 is preferable, 1 to 6 is more preferable, and 1 to 3 are 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-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2- .
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

Preferred embodiments of polyimide precursors include, as monovalent organic groups of R ¹¹³ or R ¹¹⁴ , aliphatic groups, aromatic groups and arylalkyl groups having one, two or three, preferably one acid group. Can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. 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 R ¹¹³ or R ^114, a substituent that improves the solubility of the developing solution is preferably used.
It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 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 contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl 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 cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene 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, indridin ring. , Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthalidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring, It is a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferable.

It is also preferable that the polyimide precursor has a fluorine atom in its 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 a structural unit represented by the formula (1). Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

The structural unit represented by the formula (1) is preferably the structural unit represented by the formula (1-A).
A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic radical, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent. Representing an organic group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a radically polymerizable group, and is preferably a radically polymerizable group.

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

In the polyimide precursor, the repeating structural unit represented by the formula (1) may be one kind, or two or more kinds. Further, the structural isomer of the structural unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of structural units in addition to the structural units of the above formula (1).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 1,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

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

It is preferable to include a step of precipitating a solid in the production of the polyimide precursor. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

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

<< Solvent >>
The composition (film-forming composition) used in the method for producing a film contains, as a solvent, at least two kinds of solvents having different solubilities in a polyimide precursor at 23 ° C. Specifically, as the solvent, it is preferable to use at least a mixed solvent of the solvent A having a higher solubility in the polyimide precursor and the solvent B having a lower solubility at 23 ° C. The solubility is the amount (g) of the polyimide precursor soluble in 100 g of the solvent at 23 ° C.
When there are three or more kinds of solvents, the average value of the solubility of the solvent with the highest solubility and the solubility of the solvent with the lowest solubility is obtained, and the solvent having a solubility higher than the average value is classified as solvent A, and the solubility lower than the above average value is obtained. Is classified as solvent B. Further, when there are three or more kinds of 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 specified, but can be, for example, 50 g or less. With such a configuration, convection at an early stage during drying of the 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 even more preferably 130 ° C. or higher. The upper limit is preferably 230 ° C. or lower, more preferably 210 ° C. or lower, and even more preferably 190 ° C. or lower. With such a configuration, the surface shape after coating tends to be more uniform.
The boiling point of the solvent B is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher. The upper limit is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and even more preferably 210 ° C. or lower. With such a configuration, the surface shape after coating tends to be more uniform.
It is preferable that the solvent A and the solvent B have a predetermined difference in boiling point. The difference in boiling points is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and even more preferably 20 ° C. or higher. Further, it is preferably 80 ° C. or lower. With such a configuration, the solvent B makes it possible to keep the surface shape more uniform for a long time.
In addition, in this specification, the boiling point means the temperature which boils at 1013.25 hPa.

The solvent is preferably an organic solvent.
Examples of the solvent classified into the solvent A include sulfoxides, amides, and lactams, and sulfoxides are preferable.
Examples of the solvent classified into solvent B include esters, ethers, lactones, ketones, aromatic hydrocarbons and the like. Among them, lactones or 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), alkylalkyloxyacetate (eg methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy Methyl acetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, etc.) Propyl 2-alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2- Methyl alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvate Suitable examples thereof include methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
As the amides, lactams (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone), N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

The content of the solvent is preferably such that the total solid content 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% by mass, and even more preferably 5 to 35% by mass.
The preferable range of each solvent is described. The solvent A (based on the total mass of a plurality of types, if any) is preferably 1 to 80% by mass, preferably 1 to 60% by mass in the film-forming composition. It is more preferably 5 to 40% by mass, further preferably 5 to 30% by mass. The solvent B (based on the total mass of a plurality of types) is preferably 3 to 90% by mass, more preferably 6 to 80% by mass, and 10 to 60% by mass in the film-forming composition. Is more preferable, and it is more preferably 15 to 50% by mass.
The mass ratio of the solvent A and the solvent B (based on the total mass when there are a plurality of types) is preferably 10:90 to 45:55, more preferably 15:85-40:60, and 20:80. It is more preferably ~ 30:70.

<< Surfactant >>
The film-forming composition preferably contains a surfactant.
The above-mentioned 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. Further, the surfactant preferably contains a fluoroalkylene group, and more preferably contains a perfluoroalkyl group.
The surfactant is preferably soluble in water. As used herein, "soluble" means that the solubility is 0.05% by mass or more at 23 ° C. Further, the surfactant is preferably dissolved in water at 23 ° C. in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. As an upper limit, it is practical that it is 5% by 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.
Above all, in the present invention, a perfluoroalkyl group-containing carboxylate (anionic type) is preferable from the viewpoint of increasing moisture resistance. Surfactants are preferably soluble or slightly soluble in water (eg, 0.1% by weight or more) but insoluble in hydrocarbon solvents (eg, hexane or toluene). The surface tension of the 0.1% by mass solution with respect to water is preferably 10 mN / m or more, and more preferably 15 mN / m or more. It is practical that the upper limit is 50 mN / m or less. The surface tension of the 0.1% solution with respect to PGME (propylene glycol monomethyl ether) is preferably more than 25 mN / m, more preferably 26 mN / m or more. It is practical that the upper limit is 70 mN / m or less.

Specifically, as the fluorine-based surfactants, all of them are trade names, Florinate F-C430, Florinate F-C431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-142D, Megafuck F-171. , Mega Fvck F-172, Mega Fvck F-173, Mega Fvck F-177, Mega Fvck F-183, Mega Fvck F-410, Mega Fvck F-444, Mega Fvck F-470, Mega Fvck F-471, Mega Fuck F-478, Mega Fvck F-479, Mega Fvck F-480, Mega Fvck F-482, Mega Fvck F-483, Mega Fvck F-484, Mega Fvck F-486, Mega Fvck F-487, Mega Fvck F -489, Mega Fvck F-553, Mega Fvck F-554, Mega Fvck F-556, Mega Fvck F-557, Mega Fvck F-569, Mega Fvck F-575, Mega Fvck F-780F, Mega Fvck F-781F , Megafvck R30 (above, manufactured by DIC Co., Ltd.); Ftop EF301, Ftop EF303, Ftop EF351, Ftop EF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.); Surflon S381, Surflon S382, Surflon SC101, Surflon SC105 (all manufactured by Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.); BM-1000, BM-1100 (manufactured by BMChemie) and the like.

In the case of the above-mentioned Mega Fvck series surfactant manufactured by DIC, the higher the hydrophilicity, the more preferable, and the higher the fluorine atom content, the more preferable. If the order of hydrophilicity is shown in part, F-410> F-444> F-430, F-510, F-511, F-569, F-533, F-477, F-556 >> The order is F-554. Regarding the fluorine atom content, the order is F-430> F-410, F-510, F-511> F-444 >> F-569, F-533, F-554, F-477, F-556. Become. In terms of hydrophilicity and fluorine atom content, at least one is preferably on the left side (larger) of >>, and both are preferably on the left side (larger) of >>.

Among the surfactants, Megafvck F-410 and F-444 (both trade names) showed good results in the adhesion test after PCT performed in the examples below. On the other hand, F-510 and the like were inferior. From this point of view, Megafvck F-410 and F-444 are particularly preferable, and F-444 is 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. It is practical that the lower limit value is 500 or more.
The molecular weight of the surfactant is the method described in Example 1 of Japanese Patent Application Laid-Open No. 2001-208736, specifically, asahiclean AK-225 SEC grade 1 as the mobile phase and a polymer as the SEC column. Using two PL gels 5 μm MIXED-E (inner diameter 7.5 mm, length 30 cm) manufactured by Laboratory Co., Ltd. connected in series, the mobile phase flow velocity was 1.0 ml per minute, the column temperature was 37 ° C, and the detector was It is measured by a method with a negative refractive index (RI) detector and a negative polarity.

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. It is more preferable to have. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 2% by mass or less, and may be 1% by mass or less, 0.5% by mass. % Or less, 0.1% by mass or less, and 0.01% by mass or less.
With respect to the entire composition, it is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and further preferably 0.001% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, and further 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 part by mass or more, more preferably 0.005 part by mass or more, and 0.01 part by mass or more. Is even more preferable. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, further preferably 2 parts by mass or less, and 1 part by mass. It is even more preferably less than or equal to 0.5 parts by mass or less, and even more preferably 0.1 parts by mass or less.
Only one type of surfactant may be contained, or two or more types may be contained. When two or more kinds are included, the total amount is preferably in the above range.
By adjusting the surfactant within the above range, the surface tension of the coating film of the film-forming composition can be lowered, the formation of Benard cells or its influence can be effectively suppressed, and the surface condition of the film can be improved. Therefore, it is preferable.

<< Plasticizer >>
The type of plasticizer used in the film-forming composition according to the embodiment of the present invention is not particularly specified, and known plasticizers can be used.
Specific examples thereof include phthalates, adipates, trimellitic acids, polyesters, phosphoric acids, citric acids, epoxy plasticizers, sebacic acid esters, azelaic acid esters, maleic acid esters, and benzoic acid esters. Therefore, epoxy plasticizers are preferable.
Examples of the epoxy-based plasticizer include epoxidized oil (epoxyd soybean oil, epoxidized linseed oil), epoxidized fatty acid alkyl (for example, octyl) ester and the like.
As the epoxy-based plasticizer, it is preferable to have an epoxy group of the following formula e1 or e2 in the molecule.

That is, the formula e1 is introduced at the end or in the middle of the olefin chain or paraffin chain constituting the plasticizer, the formula e2 is introduced in the middle of the chain, or both are introduced at both the end and the middle. Can be mentioned. The epoxy-based plasticizer is preferably a fatty acid or an oil or fat, and more preferably has a carboxyl group introduced into the olefin chain or paraffin chain. However, this carboxyl group may be partially or wholly esterified with an alkyl group or the like. The plasticizer preferably has 3 to 48 carbon atoms, more preferably 4 to 36 carbon atoms, and even more preferably 6 to 24 carbon atoms.
Specific examples thereof 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 has a viscosity at 25 ° C. of preferably 40 mPa · s or more, more preferably 100 mPa · s or more, and even more preferably 200 mPa · s or more. It is practical that the upper limit is 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. Is even more preferable. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 2% by mass or less, and may be 1% by mass or less, 0.5% by mass. % Or less, 0.1% by mass or less, and 0.01% by mass or less.
The content of the plasticizer with respect to 100 parts by mass of the polyimide precursor is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and preferably 0.01 part by mass or more. More preferred. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, further preferably 2 parts by mass or less, and 1 part by mass. It is even more preferably less than or equal to 0.5 parts by mass or less, and even more preferably 0.1 parts by mass or less.
The plasticizer may contain only one type or two or more types. When two or more kinds are included, the total amount is preferably in the above range.
It is preferable to set the plasticizer in the above range in order to prevent the film surface from drying, to prevent the Benard cell from continuing, and to obtain a better surface condition of the coating film.

<< Photopolymerization Initiator >>
The film-forming composition may contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.
The photoradical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the 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 at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical 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, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator 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, and 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, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
As preferred oxime compounds, the description in paragraphs 0080 to 0083 of JP2015-189883A can be referred to, and these contents are incorporated in the present specification.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, and triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.

When the photopolymerization initiator is contained, the content thereof 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. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of 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.
A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, it is possible to proceed with the polymerization reaction of the polyimide precursor as well as 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 contained, the content thereof 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 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, the total is preferably in the above range.

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

The number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically 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 radically 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 radically polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the film-forming composition preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more polymerizable groups, and at least one trifunctional or higher functional radical polymerizable compound. It is more preferable to include it. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound. The number of functional groups of the radically polymerizable compound means the number of radically polymerizable groups in one molecule.

Specific examples of the radically 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, and preferred examples thereof. Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. 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 a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogen group. Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples include polyethylene glycol di (meth) acrylate, trimethylol ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 50-006034, and Japanese Patent Application Laid-Open No. 51-037193. Such urethane (meth) acrylates, polyester acrylates described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
Further, as a preferable radical polymerizable compound other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Square Root 01-040337, and Japanese Square Root 01-040336, and JP-A-02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can also be preferably used, and their contents are incorporated in the present specification.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as other radically polymerizable compounds, and their contents are incorporated in the present specification.

Examples of the radically polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku (commercially available)). Made by A-TMMT Co., Ltd .: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups via ethylene glycol residues or propylene glycol residues. Bonded structures are preferred. These oligomer types can also be used.

Commercially available products of the radically polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains. , 231, 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-A-02-016765. , Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radically polymerizable compound, 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 phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radically polymerizable compound in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is 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.
The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacture and handling, and further excellent in developability. Moreover, the polymerizable property is good.

As the radically polymerizable compound, a monofunctional radically polymerizable compound can be preferably used. Examples of the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like (meth) ) Acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical 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 compounds other than the radically polymerizable compounds mentioned above >>>
The film-forming composition can further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

(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.

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t-valence of 1 to 200 carbon atoms, and R ¹⁰⁵ is a group represented by -OR ¹⁰⁶ or -OCO-R ^107. R ¹⁰⁶ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ indicates an organic group having 1 to 10 carbon atoms.

(In the formula, 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 is a hydrogen atom or carbon. It represents an organic group having a number of 1 to 10, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.

(In the formula, 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 Industry 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 (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. Be 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, and the like. HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, 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 lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing the low temperature curing of the composition and the warpage of the film.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of constituent units of ethylene oxide is 2 or more, and the number of constituent units is preferably 2 to 15.

Examples of epoxy compounds 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 (glycidi). Examples thereof include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.) and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it suppresses warpage and is excellent in heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.

(Oxetane compound (compound having an 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, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or individually. Two or more kinds may be mixed.

(Benzodizepine compound (compound having a benzoxazolyl group))
Since the benzoxazine compound is a cross-linking reaction derived from a cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA-type benzoxazine, B-m-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzo. Oxazine compounds can be 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.
One type of the polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<< Migration inhibitor >>
The film-forming composition preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement 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 heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compounds, hindered phenolic compounds , Pyrazole acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, 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, which is 0. .05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.
The migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in 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, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.
In addition, the following compounds 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, preferably 0.02, based on the total solid content of the film-forming composition. It is more preferably ~ 3% by mass, and even more preferably 0.05 to 2.5% by mass.
The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

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

Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011/080992, JP-A-2014-191252. The compounds described in paragraphs 0060 to 0061 of the above, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014/0975994 can be mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 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 further preferably 0, based on 100 parts by mass of the polyimide precursor. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

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

^RY1 represents an organic group having an n ^Y value (n ^Y is an integer of 1 to 12), and is preferably a hydrocarbon group. As the hydrocarbon group, a group containing an alkane (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and a group containing an alkene (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). Is more preferred, 2-3 is more preferred), groups containing aromatic hydrocarbons (6-22 carbon atoms are preferred, 6-18 are more preferred, 6-10 are even more preferred), or combinations thereof. .. Among them, ^RY1 is preferably an aromatic hydrocarbon group. ^RY1 is a substituent T (hydroxyl group, carboxyl group, amino group (NR ^N ₂ ), alkoxyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) as long as the effect of the present invention is not impaired. ~ 3 is more preferred), acyl group (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), alkoxycarbonyl group (preferably 2-12 carbon atoms, more preferably 2-6 Preferably, 2-3 are more preferred), acyloxy groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), carbamoyl groups (1-12 carbon atoms are preferred, 1-6 carbon atoms are preferred). and still more preferably 1 to 3), R ^N may have a group synonymous with the groups represented by hydrogen or R ^Y2.).
R ^Y2 to R ^Y5 each independently represent a hydrogen atom or a hydrocarbon group (preferably 1 to 36 carbon atoms, more preferably 1 to 24, 1 to 12 more preferably) represents, an alkyl group (carbon number 1 36 is preferable, 1 to 24 is more preferable, 1 to 23 is more preferable), an alkenyl group (2 to 36 carbon atoms is preferable, 2 to 24 is more preferable, 2 to 23 is more preferable), an alkynyl group (carbon number is preferable). 1-36 is preferable, 1 to 24 is more preferable, 1 to 23 is more preferable), and an aryl group (carbon number 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable).
^RY6 is an alkyl group (preferably 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, further preferably 4 to 18 carbon atoms), an alkenyl group (preferably 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, 4 to 18 carbon atoms). Is more preferred), an alkynyl group (preferably 2-36 carbons, more preferably 2-24, more preferably 4-18), an aryl group (preferably 6-22 carbons, more preferably 6-18, 6). 10 is more preferable).
n ^Y represents an integer of 1 to 12, preferably an integer of 1 to 6, and even 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 even more preferably an integer of 1 to 3.
In R ^Y2 to R ^Y6, alkyl group, alkenyl group, alkynyl group may be linear be cyclic, in the case of chain, may be linear or branched. Alkyl group, an alkenyl group, an alkynyl group, the aryl group, in the middle of the group, or the connection of the nucleus, the linking group L (carbonyl group, an oxygen atom, a sulfur atom, NR ^N, an alkylene group (carbon number 1 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, 2 to 3 is more preferable), and an arylene group (carbon number is preferable). 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), or a linking group according to a combination thereof) may be interposed.
R ^Y2 to R ^Y6 may form a ring or two of each other, respectively.
R ^Y2 to R ^Y6 may have a substituent T.

^{RY7 to RY16} are hydrogen atoms or substituents. ^However, no all R Y7 ^{to R Y9} is hydrogen atom. The substituent is preferably an organic group (preferably 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, still more preferably 1 to 12 carbon atoms), may interpose a linking group L, and has a substituent T. It is preferably a hydrocarbon group which may be present. As the hydrocarbon group, a ^RY2 group is preferable.
In the formula ^{(Y1-2), R Y7} and ^{R Y8} carboxyalkyl group (having 1 to 12 carbon atoms, more preferably 1 to 6, 1 to 3 is more preferred; the number of carboxyl groups 1-12 is preferred , 1 to 6 are more preferable, and 1 to 3 are even more preferable). The ^RY9 is preferably an aromatic group, preferably an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms). Alternatively, an alkoxycarbonyl group substituted with an aromatic group is preferable (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. , 6-18 is more preferred, and 6-14 is even more preferred).
Another preferred embodiment of formula (Y1-2) ^{are, R Y7} and ^{R Y8} alkyl group is (1 to 12 carbon atoms, more preferably 1-6, more preferably 1-3). R ^Y9 aromatic (6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10) preferably a group having, is preferably alkoxycarbonyl group having an aromatic group.
In the formula (Y1-3), ^RY11 and ^RY13 are preferably hydrogen atoms. The two of ^RY14 and ^RY15 may be combined to form a substituent in the form of = C (NR ^N ₂ ) ₂ (= means that it is bonded to a nitrogen atom by a double bond).
In Formula ^{(Y1-4), R Y13} is preferably a hydrogen ^{atom, R Y10, R Y11, R} Y12, R Y16 represents an alkyl group (having 1 to 12 carbon atoms, more preferably 1 to 6, 1 ~ 3 is more preferable). In this ^case, it is preferable that a ^{R Y11} and ^{R Y16, R Y10} and ^{R Y12} are bonded to form a ring bicyclo compound. Specific examples thereof include diazabicyclononene and diazabicycloundecene.

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

In the present embodiment, the electron-attracting group means that the substituent constant σm of Hammett shows a positive value. Here, σm is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ CO groups (σm = 0.63), HC≡C groups (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. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In the formulas (EWG-1) to (EWG-6), R ^{x1 to} R ^x3 independently contain a hydrogen atom and an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3). More preferably), an alkenyl group (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), an aryl group (preferably 6-22 carbon atoms, more preferably 6-18, 6-18 10 is more preferred), a hydroxyl group, or a carboxyl group. Ar represents an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more 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 groups, alkenyl groups, aryl groups, and Ar may have a substituent T as long as the effects of the present invention are not impaired. Among them, Ar preferably has a carboxyl group (preferably 1 to 3). * Represents the bond position.
L ¹ is a linking group L group having the same meaning ^{as, -CR X2 R X3 -, -} Ar 1 -, it is preferably a group formed by combining these groups. Ar ¹ is an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms).
Np represents an integer of 1 to 6, with an integer of 1 to 3 being preferred, and 1 or 2 being more preferred.

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 acidic compounds that generate bases when heated to 40 ° C. or higher and ammonium salts having pKa1 of 0 to 4 anions and ammonium cations described in International Publication No. 2015/199219. These contents are incorporated herein by reference.

When a 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, further preferably 5% by mass or less.
As the thermosetting accelerator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range. Further, the film-forming composition may be configured to be substantially free of a thermosetting accelerator. The term "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.

<< Photo-curing accelerator >>
The film-forming composition may contain a photocuring accelerator. The photocuring accelerator preferably generates a base by exposure and does not show activity under normal conditions of normal temperature and pressure, but when an electromagnetic wave is irradiated and heated as an external stimulus, the base (base) is used. It is preferable that it generates (sexual substance). Since the base generated by exposure acts as a catalyst when the polyimide precursor is cured by heating, it can be preferably used. The preferred conditions for exposure are the same as those specified in the exposure step described later.
A known photocuring accelerator can be used. For example, the basic component was neutralized by forming a salt, such as a transition metal compound complex, one having a structure such as an ammonium salt, or one in which the amidin moiety was latent by forming a salt with a carboxylic acid. Examples thereof include ionic compounds and nonionic compounds in which a base component is 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 carbamic acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, JP-A-2006-189591 and special publications. A photocuring accelerator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, and having an oxime structure and a carbamoyl oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581. Examples thereof include, but are not limited to, a photocuring accelerator, and other known photocuring accelerator structures can be used.

Other examples of the photocuring accelerator include the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples thereof include the compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204319, and the compounds described in paragraph 0052 of International Publication No. 2010/064631.

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 a 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, further preferably 20% by mass or less.
As the photocuring accelerator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Other additives>
As long as the effect of the present invention is not impaired, the film-forming composition contains various additives such as a thermoacid generator, a sensitizing dye, a chain transfer agent, and a surfactant other than those described above, as required. Higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended. When these additives are blended, 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 thermoacid generator. The thermoacid generator generates an acid by heating, promotes the cyclization of the polyimide precursor, and further improves the mechanical properties of the film. Examples of the thermoacid generator include the compounds described in paragraph 0059 of JP2013-167742A. The preferable range of the heating temperature (acid generation temperature) of the thermoacid generator is the same as the temperature specified in the heating step described later.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polyimide precursor. By containing 0.01 part by mass or more of the thermal acid generator, the crosslinking 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. The content of the thermoacid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less from the viewpoint of electrical insulation of the film.
Only one type of thermoacid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<< Sensitive Dye >>
The film-forming composition may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron excited state. The sensitizing dye in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the film-forming composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the film-forming composition. It is more preferably 15% by mass, and even more preferably 0.5 to 10% by mass. The sensitizing dye may be used alone or in combination of two or more.

<< Chain Transfer Agent >>
The film-forming composition may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, 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 and 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the film-forming composition. Parts are more preferable, and 1 to 5 parts by mass are further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

<< Higher fatty acid derivatives >>
In the film-forming composition, in order to prevent polymerization inhibition due to oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide are added and unevenly distributed on the surface of the composition during the drying process after application. You may.
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. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

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

From the viewpoint of insulating properties, the metal content of the film-forming composition is preferably less than 5 parts by mass (parts per million), more preferably less than 1 parts by mass, still more preferably less than 0.5 parts by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the film-forming composition, a film-forming composition is formed by selecting a raw material having a low metal content as a raw material constituting the film-forming composition. Examples thereof include a method of filtering the raw material to be used, a method of lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.

From the viewpoint of wiring corrosiveness, the film-forming composition preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

A conventionally known storage container can be used as the storage container for the film-forming composition. In addition, as the storage container, for the purpose of suppressing impurities from being mixed into the raw materials and compositions, the inner wall of the container is made of a multi-layer bottle composed of 6 kinds of 6 layers of resin, and 6 kinds of resins are made into a 7 layer structure. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Preparation of composition>
The film-forming composition can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
Further, 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 diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. 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 diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure 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 has an exposure step of exposing and a developing step of developing the exposed film after the film forming step. After this development, the exposed film can be further cured by heating.

Further, in order to form a laminate, after forming the film according to the above-mentioned film manufacturing method, the film forming step and heating step, the film forming step, the exposure step, and the developing step (if necessary, further heating step) are further formed. ) Is preferably performed in the above order. In particular, it is preferable to carry out 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 in which the films are laminated a desired number of times. It is also preferable to apply a metal layer when forming a laminate.

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

In the method for producing a film of the present invention, it is preferable to use a slit coater as a means for applying the film-forming composition to a 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. The upper limit is preferably 250 μm or less, more preferably 200 μm or less, and further preferably 150 μm or less.
The slit gap is preferably 30 μm or more, more preferably 50 μm or more, and even more preferably 70 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 120 μm 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. The upper limit is preferably 500 mm / s or less, more preferably 400 mm / s or less, and even more preferably 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. The upper limit is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 50 μm or less.

<< Drying process >>
The production method of the present invention may include a step of drying to remove the solvent after the film is formed. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 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. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less. This thickness is the same for the film thickness after the heating step described later.

<< Exposure process >>
Exposure dose in the exposure step, for example, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, it is more preferable to irradiate 200~8000mJ / cm ^2.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.
In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (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 Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. For the film-forming composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.

<< Development process >>
The developing method in the developing step is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
Development is preferably carried out using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) 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, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acid acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene. As the sulfoxides, dimethyl sulfoxide is preferably mentioned.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developer preferably has 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly specified, but is usually 20 to 40 ° C.
After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with the solvent contained in the film-forming composition. The rinsing 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., further preferably 140 to 400 ° C., and even more preferably 160 to 350 ° C.
The heating is preferably performed at a heating rate 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 rise rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the film remains. The stress can be relieved.
The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the film-forming composition is applied onto a substrate and then dried, the temperature after drying is, 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 to gradually raise the temperature from.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
In particular, when forming a multi-layered laminate, 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. The reason is not clear, but it is considered that the ethynyl groups of the polyimide precursors between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, 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, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing 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 forming process >>
A metal layer may be applied to the surface of the film of the film-forming composition after the development treatment to form the film.
As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More 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-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<< Laminating process >>
The laminating step also includes performing the film forming step and the heating step, or the film forming step, the exposure step, and the developing step again on the surface of the film or the metal layer of the film forming composition in the above order. Good. The laminating step may further include the above-mentioned drying step, heating step, and the like.
When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.
The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a structure in which the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
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 step and the exposure of the film forming composition so as to further cover the metal layer. It is preferable that the steps and the above-mentioned developing step (more heating step if necessary) are performed in the above-mentioned 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) of the film-forming composition and the metal layer 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 to form 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 taken into account, the contents of which are incorporated herein by reference.

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. Further, a method for manufacturing a semiconductor device in which chips are arranged in a laminate of the present invention will be disclosed. Regarding the chips and the method of arranging the chips here, the description of the three-dimensional mounting technology of semiconductors, Seiichi Denda, CQ Publisher, published on June 1, 2011 can be taken into consideration, and these contents are incorporated in the present specification. ..

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis example 1>
[Synthesis of polyimide precursor resin A-1 from pyromellitic acid 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 in 50 mL of N-methylpyrrolidone. Suspended in and dried with a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained a few minutes after heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) thionyl chloride was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. The viscosity increased while adding thionyl chloride. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. 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 water in a drying reactor equipped with a flat bottom joint 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. The mixture was then cooled to −20 ° C. and then 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, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent liquid by dropping over 1 hour. Viscosity increased while adding 4,4'-diaminodiphenyl ether. Then 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 at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. 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]
10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 3,3', 4,4 while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 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. The mixture was then cooled to −20 ° C. and then 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, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of NMP in the obtained transparent liquid, and the mixture was added dropwise over 1 hour. Viscosity increased while adding 4,4'-diaminodiphenyl ether. Then 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 at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days. This polyimide precursor had Mw = 24300 and Mn = 9500.

<Preparation of film-forming composition>
The film-forming compositions of Examples and Comparative Examples were prepared as a uniform solution by blending at the ratio (part by mass) shown in the table below. In the examples described below, the obtained composition was filtered and used using a polyethylene filter having a pore size of 0.8 μm.

<Film formation by slit coat>
As a substrate, a substrate obtained by sputtering 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 was prepared. A coating film of the film-forming composition prepared above using a slit coater (LC-R300G manufactured by SCREEN Finetech Solutions Co., Ltd., but the slit head width is set to 100 mm and the coating length is set to 100 mm) on the surface of this substrate. Was formed. The detailed conditions of the slit coater device are as shown in the table below. This was left at 23 ° C. and a reduced pressure of 50 Pa for 5 minutes, and then dried on a hot plate at 100 ° C. for 5 minutes. The coating film thickness (after drying) was measured every 10 mm from a position of 10 mm from the end of the coated portion using an F20 film thickness measuring system manufactured by Filmometrics, and the average value was taken. At the time of film formation, the nozzle head was immersed in the dipping solution under the conditions shown in the table below in the head standby step. Further, after the film formation, the nozzle head was immersed in the cleaning liquid in the head cleaning step. The temperature at the time of immersion and washing was (normal temperature (23 ° C.)).

<Applicability>
The applicability at the time of the slit coating was evaluated. The coating film formed on the substrate is left at 23 ° C. and a reduced pressure of 50 Pa for 5 minutes, dried on a hot plate at 100 ° C. for 5 minutes, and then visually observed to see if cissing or streaks are observed. confirmed. The observation area was the entire surface excluding 10 mm from the end face of the coated portion. In each Example and Comparative Example, the average value of three samples was adopted.
Uniform with few or no repellents and streaks: Good repellents and streaks were slightly observed but generally uniform: Good repellents and streaks were common: Substandard

<Surface after coating and drying>
The surface shape after application 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, the average value of three samples was adopted.
Fluorescent lamps appear to be mirror-reflected as they are in the entire coating area-Gloss: Excellent Fluorescent lamps appear blurry in at least part of the coating area-Weak Yuzu skin: Good Fluorescent lamps appear blurry in the entire coating area- Yuzu skin: Substandard

<In-plane uniformity after application 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 with the coating film (after drying) is measured by a film thickness measuring device (F20 film thickness measurement system manufactured by Philmetrics), 90 mm in length and 90 mm in width excluding the 10 mm at the end of the coating. 81 points were measured in the 90 mm region at intervals of 10 mm, and the maximum and minimum differences were defined as TTV (Total thickness variation). In each Example and Comparative Example, the average value of three samples was adopted.
The TTV was measured in a region excluding 10 mm from the end of the coated portion.
≤1 μm: Excellent> 1 μm, ≤2 μm: Good> 2 μm: Substandard

<Drying time after application>
In the above drying step, the time from placing on the hot plate to drying was evaluated. When the specified time elapses, the surface of the coated part is touched with a cotton swab, and if a trace remains, the drying is not completed, and if no trace remains, the drying is completed. In each Example and Comparative Example, the average value of three samples was adopted. The measurement was a drying time at 100 ° C.
≤300 sec: Excellent> 300 sec, ≤400: Good> 400 sec: Substandard

<Nozzle head dirt after cleaning the nozzle head>
In the above film forming step, a cleaning solution 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 solution. The dirt on the head was evaluated. In each example and comparative example, it was adopted in three tests. The measurement was a drying time at 100 ° C.
Dirt was not confirmed 3 times: None Dirt was confirmed 1 or more times out of 3 times: Yes

<Member adhesion of coating film (shear test)>
A shear test was performed on the dried coating film formed by the slit coating on the various substrates shown in Tables 1 to 9. The measuring device (Condor Sigma bond tester manufactured by XYZTEC) was used. In the test, the film dried after being applied to the substrate was exposed to 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 from the side surface at 10 μm / s (a needle set at a position 5 μm from the substrate). In each Example and Comparative Example, the average value of three samples was adopted.
<10 g: Substandard ≧ 10 g, <40 g: Good ≧ 40 g: Good The same shear test was performed on a Cu-plated substrate, an Al—Si—Cu alloy-plated substrate, a Ti sputtered substrate, and a Ni sputtered substrate with a coating film. .. Further, for 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>
In addition, a PCT (pressure cooker test) was performed on a Cu-plated substrate and a Ti-sputtered substrate to which a coating film was attached. A PCT test device (EHS-412M, manufactured by ESPEC) was used. The treatment conditions for the coating film were 121 ° C., 100% relative humidity (RH), and 500 hours. The coated film after the treatment was evaluated for adhesion (shear test) under the same conditions as the above-mentioned <member adhesion of coating film> test. The evaluation criteria are the same.

sec: seconds, min: minutes * 1 Immersion: Head standby Immersion: Immersion 30 seconds after application, discharge 30 seconds after immersion * 2 Comparative example 2: * If DMSO is 100%, it cannot be dried by absorbing moisture in the air. : Could not be applied because the solid content could not be dissolved in the solvent Unmeasurable: Could not be measured because it could not be applied Unable to perform: Adhesion test could not be performed because it could not be applied

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

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

(C) Photoradical polymerization initiator C-1: IRGACURE OXE-01 manufactured by BASF, Inc.
C-2: The following compounds

(D) Radical Polymerizable Compound D-1: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.
D-2: SR-209 (Tetraethylene glycol dimethacrylate, manufactured by Sartmer)

(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 Adhesive Improvement Agent (Silane Coupling Agent)
G-1: Made by Shin-Etsu Chemical Co., Ltd., Part number: KBM-602
G-2: The following compound (Et represents an ethyl group in the formula)

(H) Curing accelerator (thermobase generator)
H-1: The following compounds
H-2: The following compounds

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

As can be seen from the above results, in the present invention, when the slit coating is carried out, a film containing a polyimide precursor, a specific solvent, a surfactant or a plasticizer is applied as the film-forming composition to be applied. Even when the coating film was formed on the metal surface, a good surface shape 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 drying, the drying time after coating, the nozzle head stain after cleaning the nozzle head, and the member adhesion of the coating film are also obtained. Good performance was obtained.

<Examples of exposure and development>
The film-forming composition prepared in Example 1 was coated on a copper wafer (corresponding to a metal layer and a member containing metal) with a slit coat 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 pre-cured film (film of a film-forming composition) having a thickness of about 15 μm. This was exposed using an aligner (Karl-Sus MA150 [trade name]) through a mask with a line-and-space pattern (step: 5-20 μm). The exposure was carried out 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 pre-cured film after exposure was dissolved in cyclopentanone for 75 seconds and paddle-developed. The line width of the developed part was evaluated according to the following criteria. It was confirmed that the exposure width of the base substrate after development was within ± 10% of the mask size, and that good exposure development was possible.
The formed resin pattern was heated at 250 ° C. for 3 hours, and the polyimide precursor was allowed to undergo a cyclization reaction to form a polyimide resin, whereby an extremely stable and strong resin pattern was obtained even though it was a fine pattern. ..
Since the produced resin pattern is made of polyimide, it has excellent insulating properties, and as described above, it is compatible with metals and can be suitably used for fine processing. Therefore, WL-CSP (WL-CSP) It was found to be particularly suitable for the production of rewiring layers (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 carried out in the same manner. An excellent effect was obtained as in Example 1. 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 carried out 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 part 21a Resin 24 Roller 25 Roller bat 25b Draining blade 25a Cleaning liquid 26 Maintenance part 100 Slit coating device

Claims (23)

Polyimide precursor and
At least two solvents having different solubilities at 23 ° C. for the polyimide precursor,
Using a composition comprising at least one selected from the group consisting of surfactants and plasticizers.
A method for producing a film, which comprises a step of performing a slit coating on a member, wherein the member contains at least a part of a metal. The method for producing a membrane 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, which comprises a head cleaning step of cleaning the nozzle head with a cleaning liquid after the step of performing slit coating. The step of performing the slit coating 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 common to the cleaning liquid in an amount of 90% by mass or more. 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 the 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 membrane according to any one of claims 3 to 5, wherein the cleaning liquid contains the 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 the 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 the 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, further comprising an exposure step of exposing the film formed by the slit coating and a developing 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 method for producing a laminate according to claim 11, which comprises a step of applying a metal layer to the film. A method for manufacturing a semiconductor device in which a chip is placed 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 chips are arranged on a laminate manufactured by the method according to claim 11 or 12. A composition for forming a film used in the production method according to any one of claims 1 to 10, wherein the polyimide precursor and at least two kinds of solvents having different solubilities in the polyimide precursor at 23 ° C. , A film-forming composition comprising at least one selected from the group consisting of surfactants and plasticizers. The film-forming composition according to claim 15, wherein the polyimide precursor is a dicarboxylic acid or a condensate of a dicarboxylic acid derivative and a diamine. Of the at least two kinds of solvents, the solvent having the highest solubility of the polyimide precursor is a solvent of sulfoxides, and among the at least two kinds of solvents, the solvent having the lowest solubility of the polyimide precursor is a ketone or The film-forming composition according to claim 15 or 16, which is a solvent for lactones. Of the at least two kinds of solvents, the total mass of the solvent in which the solubility of the polyimide precursor is higher than the following average value, and the solvent of the at least two kinds of solvents in which the solubility of the polyimide precursor is lower than the following average value. The film-forming composition according to any one of claims 15 to 17, wherein the total mass ratio is 10:90 to 45:55;
The average value is the average value of the solubility of the solvent having the highest solubility at 23 ° C. of the polyimide precursor and the solubility of the solvent having the lowest solubility at 23 ° C. of the polyimide precursor. 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.