TWI862487B - Film manufacturing method, laminate manufacturing method, semiconductor device manufacturing method and film forming composition - Google Patents

Abstract

The present invention provides a method for manufacturing a film, which includes a process of slit coating on a component using a composition, wherein the component at least partially contains a metal, and the composition contains: a polyimide precursor; at least two solvents having different solubility at 23°C relative to the polyimide precursor; and at least one selected from the group consisting of a surfactant and a plasticizer. Furthermore, the present invention relates to a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film-forming composition related to the method for manufacturing the film.

Description

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

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

Polyimide resin has excellent heat resistance and insulation properties, so it is suitable for various uses. The use is not particularly limited, but if the actual semiconductor device for mounting is taken as an example, it can be used as a material for an insulating film or a sealing material or as a protective film. In addition, it is also used as a base film or cover layer of a flexible substrate, etc.

The above-mentioned polyimide resin generally has low solubility in solvents. Therefore, a method of dissolving the polyimide precursor in a solvent before cyclization is often used. In this way, excellent operability can be achieved, and when manufacturing various products such as the above, it can be coated on a substrate and processed in various forms. Then, the polyimide precursor is heated to form a cured product. In addition to the high performance of polyimide resin, from the perspective of excellent adaptability in such manufacturing, its industrial application development is increasingly expected.

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

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2013-243121

Here, as described in the above-mentioned patent document 1, a technique for forming a composition containing a polyimide precursor into a film by slit coating is known. However, it is known that when the object of slit coating of the polyimide precursor composition contains metal on its surface, so-called "orange peel" may sometimes be generated on the surface of the film.

The purpose of the present invention is to solve the above-mentioned problems, and to provide a method for manufacturing a film using a narrow coating that can suppress the generation of "orange peel" and achieve a good surface shape even when a coating film is formed on a metal surface, a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film-forming composition suitable for use in these manufacturing methods.

Based on the above-mentioned topic, the inventors have conducted research and found that when a composition containing a polyimide precursor is applied in a layer by a slit coating method, cells are generated during drying and the surface is orange peel-like. In addition, it is found that in the composition containing a polyimide precursor (film-forming coating liquid), at least two solvents with different solubility at 23°C relative to the polyimide precursor are used as solvents, and at least one selected from the group including surfactants and plasticizers is blended into the above-mentioned composition, thereby solving the above-mentioned topic.

Specifically, the above-mentioned problem is solved by the following mechanism <1>, preferably by <2> to <23>.

<1> A method for manufacturing a film, comprising a process of slit coating a component using a composition, wherein the component at least partially contains a metal, and the composition contains: a polyimide precursor; at least two solvents having different solubility at 23°C relative to the polyimide precursor; and at least one selected from the group consisting of a surfactant and a plasticizer.

<2> The method for producing a film as described in <1>, wherein the surfactant is a compound containing a perfluoroalkyl group with a weight average molecular weight of 5,000 or less and is soluble in water.

<3> A method for manufacturing a film as described in <1> or <2>, which includes a nozzle cleaning process of cleaning the nozzle head with a cleaning liquid after performing a slit coating process.

<4> The method for manufacturing the film as described in <3>, wherein the process for performing slit coating includes a nozzle standby process, in which the nozzle head is immersed in an immersion liquid, and the immersion liquid is a liquid having a composition equal to or greater than 90% by mass to the cleaning liquid.

<5> The method for producing a membrane as described in <3> or <4>, wherein the cleaning solution contains the solvent with the highest solubility in the polyimide precursor at 23°C among the at least two solvents.

<6> A method for producing a membrane as described in any one of <3> to <5>, wherein the cleaning solution contains the solvent with the lowest solubility in the polyimide precursor at 23°C among the at least two solvents.

<7> The method for producing a membrane as described in <4>, wherein the impregnation solution contains the solvent with the highest solubility in the polyimide precursor at 23°C among the at least two solvents.

<8> The method for producing a membrane as described in <4> or <7>, wherein the impregnation solution contains the solvent with the lowest solubility in the polyimide precursor at 23°C among the at least two solvents.

<9> A method for producing a film as described in any one of <1> to <8>, which comprises an exposure process for exposing the film formed by the above-mentioned slit coating and a development process for developing the exposed film.

<10> The method for manufacturing a film as described in any one of <1> to <9>, further comprising a heating process of heating the film.

<11> A method for manufacturing a laminate, wherein the method for manufacturing a film described in any one of <1> to <10> is performed multiple times.

<12> The method for manufacturing a laminate as described in <11> further includes a process for applying a metal layer to the above-mentioned film.

<13> A method for manufacturing a semiconductor device, wherein a film is configured on a wafer manufactured by any of the methods described in <1> to <10>.

<14> A method for manufacturing a semiconductor device, wherein a multilayer body is configured as a chip manufactured by the method described in <11> or <12>.

<15> A film-forming composition used in the production method described in any one of <1> to <10>, the film-forming composition comprising a polyimide precursor, at least two solvents having different solubility at 23°C relative to the polyimide precursor, and at least one selected from the group consisting of a surfactant and a plasticizer.

<16> The film-forming composition as described in <15>, wherein the polyimide precursor is a condensate of a dicarboxylic acid or a dicarboxylic acid derivative and a diamine.

<17> The film-forming composition as described in <15> or <16>, wherein among the at least two solvents, the solvent with the highest solubility of the polyimide precursor is a sulfone solvent, and among the at least two solvents, the solvent with the lowest solubility of the polyimide precursor is a ketone or lactone solvent.

<18> The film-forming composition as described in any one of <15> to <17>, wherein the ratio of the total mass of the solvents in the at least two solvents whose solubility of the polyimide precursor is higher than the following average value to the total mass of the solvents in the at least two solvents whose solubility of the polyimide precursor is lower than the following average value is 10:90~45:55; the above average value is the average value of the solubility of the solvent with the highest solubility of the polyimide precursor at 23°C and the solubility of the solvent with the lowest solubility of the polyimide precursor at 23°C.

<19> A film-forming composition as described in any one of <15> to <18>, wherein the surfactant contains fluorine atoms.

<20> The film-forming composition as described in <19>, wherein the surfactant is a compound containing a perfluoroalkyl group with a weight average molecular weight of 5,000 or less and is soluble in water.

<21> A film-forming composition as described in any one of <15> to <20>, wherein the content of the above-mentioned surfactant in the solid component is 0.005-2% by mass.

<22> A film-forming composition as described in any one of <15> to <21>, wherein the plasticizer is epoxidized oil.

<23> A film-forming composition as described in any one of <15> to <22>, wherein the content of the plasticizer in the solid component is 0.005 to 2% by mass.

According to the present invention, in the case of narrow slit coating, even when a resin coating film is formed on the metal surface, the generation of "orange peel" can be suppressed and a good surface shape can be achieved.

21: Nozzle head

22: Nozzle cleaner

23: Transportation Department

21a: Resin

24: Roller

25: Roller groove

25b: Liquid removal scraper

25a: Cleaning fluid

26:Maintenance Department

30: Substrate

100: Narrow seam coating device

d1~d5: Direction

FIG. 1 is a process diagram (1) for illustrating a preferred embodiment of slit coating applicable to the present invention by means of a schematic side view.

FIG. 2 is a process illustration diagram (2) for illustrating a preferred embodiment of slit coating applicable to the present invention by means of a schematic side view.

FIG3 is a process illustration diagram (3) for illustrating a preferred embodiment of slit coating applicable to the present invention by means of a schematic side view.

The description of the constituent elements of the present invention described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

Regarding the marking of groups (atomic groups) in this specification, the marking without description of substituted and unsubstituted includes both those without substitution and those with substitution. For example, "alkyl" includes not only alkyl without substitution (unsubstituted alkyl), but also alkyl with substitution (substituted alkyl).

In this specification, "exposure" includes exposure using electron beams, ion beams, and other particle beams, in addition to exposure using light, unless otherwise specified. In addition, as light used for exposure, usually, active light or radiation such as mercury lamp bright line spectrum, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, etc. can be cited.

In this manual, the numerical range indicated by "~" refers to the range that includes the numerical values written before and after "~" as the lower limit and upper limit.

In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either one of them, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid" or either one of them, and "(meth)acryl" means both "acryl" and "methacryl" or either one of them.

In this manual, the term "process" refers not only to independent processes, but also to processes that cannot be clearly distinguished from other processes as long as the expected effects of the process can be achieved.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined based on gel permeation chromatography (GPC) and are defined as styrene-equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using one or more of the guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as the column. Unless otherwise specified, the eluent is determined using THF (tetrahydrofuran). In addition, unless otherwise specified, the detection is set to use a UV (ultraviolet) detector with a wavelength of 254nm.

The shapes, sizes, quantities, and configuration locations shown in the drawings are arbitrary and not limited.

The method for producing the film of the present invention is characterized in that it includes a process of slit coating on at least a portion of a component containing metal using a composition containing a polyimide precursor, at least two solvents having different solubility at 23°C relative to the polyimide precursor, and at least one selected from the group including a surfactant and a plasticizer. Thus, in the slit coating, even if a coating film is formed on the metal surface, the generation of "orange peel" can be suppressed and a good surface shape (gloss) can be achieved.

The polyimide precursor is heated and hardened after being formed into a coating film. That is, it is presumed that the coating film is in a fluid liquid state at the coated stage, and as a result, orange peel is generated. Moreover, it is presumed that it is important to consider the following aspects when suppressing orange peel.

(1) using a low-solubility solvent in addition to a high-solubility solvent to suppress convection at an early stage in drying, and (2) using a surfactant to reduce the surface tension of the coating film, or (3) adding a plasticizer to avoid the situation where the surface is pre-dried and internal convection continues

Moreover, as described above, by using two or more solvents with different solubility and using at least one selected from the group including surfactants and plasticizers, orange peel is suppressed and the surface shape is improved. Furthermore, it is also successful in improving the adhesion between the polyimide resin layer and the metal (for example, the metal layer). In particular, by using a specified surfactant, it is also successful in obtaining excellent adhesion with copper (for example, the copper layer).

The present invention is described in detail below.

<Narrow seam painting>

FIG. 1 is a process description diagram (1) for illustrating a preferred embodiment of slit coating applicable to the present invention by means of a schematic side view. The coating device 100 of this embodiment has a conveying section 23 for conveying a substrate 30 and a support table (not shown) for supporting the substrate from below. An anti-etching agent (resin) 21a is ejected from a nozzle head 21 through a slit-shaped nozzle on the substrate 30, and the substrate 30 is conveyed in a direction d3 (slit coating process). The conveying section 23 can be composed of a plurality of conveying rollers and a conveying roller driving section for rotating the conveying rollers. The nozzle head 21 can be raised and lowered in the vertical direction according to the timing of the conveying unit conveying the substrate 30. Similarly, the support table (not shown) can also move and retreat from directly below the nozzle head. At this time, the nozzle head can be put on standby and wait for the next substrate to be conveyed (nozzle standby process). During the nozzle standby process during the slit coating process or after the slit coating process, the nozzle head can be immersed (immersion treatment process) or cleaned (nozzle cleaning process) as shown below.

In the device 100 of this embodiment, a nozzle cleaner 22 is arranged directly below the nozzle. When the resin is ejected onto the substrate, the nozzle is lowered vertically relative to the coating surface (d1) and the nozzle 21 is immersed in the immersion liquid in the nozzle cleaner 22 (Figure 2). The time for immersing the nozzle in the immersion liquid in the cleaner is preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and even more preferably 0.5 minutes or more. As an upper limit, 10 minutes or less is preferably, 8 minutes or less is more preferably, and 5 minutes or less is even more preferably. In this way, the front end of the nozzle 21 can be cleaned.

FIG3 is a side view of a device for explaining a nozzle maintenance process different from FIG1 and FIG2, and shows a maintenance (cleaning) state of the nozzle head. The device of this embodiment is provided with a roller 24 that rotates in the direction d2. The roller tank 25 is filled with a cleaning liquid 25a so as to immerse the lower part of the roller 24. The device 100 of this embodiment is also provided with a liquid removal scraper 25b. The roller 24 and the roller tank 25 constitute a maintenance portion 26. The maintenance portion can be raised and lowered in a vertical direction relative to the substrate surface. The device of this embodiment is equipped with such a maintenance unit, so that during the maintenance process, the nozzle head 21 can be maintained (cleaned) by raising the maintenance unit 26 by d4 without lowering the nozzle head 21 by d5. In the maintenance unit, the liquid flowing from d5 is replaced with a cleaning liquid. The time for the cleaning liquid to flow to the nozzle head is preferably more than 1 minute, more preferably more than 2 minutes, and more preferably more than 5 minutes. As an upper limit, less than 120 minutes is preferably, less than 60 minutes is more preferably, and less than 30 minutes is more preferably. In this way, the nozzle head 21 can be cleaned.

In the present invention, as described above, in the process of performing slit coating, it is preferred to include a nozzle standby process. In the nozzle standby process, it is preferred that the nozzle is immersed in an immersion liquid. The immersion liquid is preferably a liquid having the same composition as the cleaning liquid at 90% by mass or more, more preferably a liquid having the same composition at 95% by mass or more, and more preferably the same composition.

Regarding the type of compound or the mixing ratio of the immersion liquid and the cleaning liquid, it is preferred that the liquid have the same composition as the solvent in the film-forming composition at 90% by mass or more, more preferred that the liquid have the same composition at 95% by mass or more, and even more preferred that the same composition.

The cleaning solution also preferably contains the solvent with the highest solubility at 23°C of the polyimide precursor among at least two solvents contained in the film-forming composition. Furthermore, the cleaning solution preferably contains the solvent with the lowest solubility at 23°C of the polyimide precursor among at least two solvents contained in the film-forming composition. Furthermore, it is more preferred that the cleaning solution contains both the solvent with the highest solubility at 23°C of the polyimide precursor and the solvent with the lowest solubility at 23°C of the polyimide precursor among at least two solvents contained in the film-forming composition.

The immersion liquid also preferably contains the solvent with the highest solubility at 23°C of the polyimide precursor among at least two solvents contained in the film-forming composition. In addition, the immersion liquid preferably contains the solvent with the lowest solubility at 23°C of the polyimide precursor among at least two solvents contained in the film-forming composition. Furthermore, it is more preferred that the immersion liquid contains both the solvent with the highest solubility at 23°C of the polyimide precursor and the solvent with the lowest solubility at 23°C of the polyimide precursor among at least two solvents contained in the film-forming composition.

In addition, regarding slit coating and devices applicable thereto, reference can be made to Japanese Patent Publication No. 2009-070973, and the contents described therein are incorporated into this manual.

<Membrane-forming composition>

<<Polyimide precursor>>

As a polyimide precursor, it is preferred to contain a repeating constituent unit (constituent unit) represented by the following formula (1).

^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 are independently an oxygen atom or NH, preferably an oxygen atom.

<<<R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group comprising a combination thereof, preferably a linear aliphatic group having 2 to 20 carbon atoms, 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 comprising a combination thereof, and more preferably an aromatic group having 6 to 20 carbon atoms.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

Specifically, the diamine preferably contains 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 group containing such combinations. The diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. As examples of aromatic groups, the following aromatic groups can be cited.

In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and combinations thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, and -SO ₂ -; and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -.

As the diamine, specifically, there can be mentioned 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexane, Hexylmethane and isophoronediamine; meta-phenylenediamine and para-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenyl) Biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4' -Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-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'-diaminodiphenyl phenylmethane, 2-(3',5'-diaminobenzyloxy)ethyl methacrylate), 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 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]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethyl) At least one diamine selected from the group consisting of 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’,6,6’-hexafluorotoluidine and 4,4’-diaminoquaternaryl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemistry 3]

As a preferred example, a diamine having at least two alkylene glycol units in the main chain can also be cited. Preferably, it is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, or both, and more preferably, it is a diamine that does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) (mark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are not limited to these.

The following shows the structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176.

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

R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -, wherein Ar ⁰ is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and L ⁰ is defined the same as the group of A above, and the preferred range is also 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, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

^R58 and ^R59 are independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of diamine compounds that impart the structure of formula (51) or formula (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One of these compounds may be used, or two or more of them may be used in combination.

<<<R ¹¹⁵ >>>

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

The definition of R ¹¹² is the same as that of A, and the preferred range is also the same.

Regarding the tetravalent organic group represented by R ¹¹⁵ in formula (1), specifically, there can be mentioned the tetracarboxylic acid residual group remaining after removing the dianhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. It is preferred that the tetracarboxylic dianhydride is a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same definition as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 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)propanetetracarboxylic dianhydride, anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one of their alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

In addition, the tetracarboxylic dianhydride (DAA-1) to (DAA-5) shown below can also be cited as a better example.

<<<R ¹¹³ and R ¹¹⁴ >>>

In formula (1), ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of ^R113 and ^R114 contains a free radical polymerizable group, and it is more preferred that both contain a free radical polymerizable group. The free radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a free radical, and a group having an ethylenic unsaturated bond is a preferred example.

As the group having an ethylenic unsaturated bond, there can be cited a vinyl group, an allyl group, a (meth)acryl group, a group represented by the following formula (III), etc.

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

In formula (III), ^R201 represents an alkylene group having 2 to 12 carbon atoms, _-CH2CH (OH) _CH2- , or a (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly)oxyalkylene group refers to an oxyalkylene group or a polyoxyalkylene group.

Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and -CH ₂ CH(OH)CH ₂ -, with ethylene, propylene, trimethylene, and -CH ₂ CH(OH)CH ₂ - being more preferred.

It is particularly preferred that R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

In a preferred embodiment of the polyimide precursor, the monovalent organic group of R ¹¹³ or R ¹¹⁴ includes a group having 1, 2 or 3 acid groups, preferably an aliphatic group, an aromatic group, and an aralkyl group having 1 acid group. Specifically, an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms and an acid group may be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group may 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 in a developer solution can be preferably used.

From the viewpoint of solubility in aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, ^R113 or ^R114 is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms in the alkyl group is preferably 1 to 30 (or more than 3 when cyclic). The alkyl group may be any of a straight chain, a branched chain, or a cyclic chain. Examples of the straight chain or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. 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 cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As polycyclic alkyl groups, for example, adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, bornadiyl, bicyclohexyl and pinenyl can be cited. Among them, cyclohexyl is the best from the perspective of both taking into account the sensitivity and the sensitivity. In addition, as the alkyl group substituted by an aromatic group, a linear alkyl group substituted by an aromatic group described below is preferred.

環、三伸苯環、茀環、聯 苯環、吡咯環、呋喃環、噻吩環、咪唑環、

唑環、噻唑環、吡啶環、吡

環、嘧啶環、噠

環、吲哚

環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹

環、喹啉環、酞

環、萘啶環、喹

啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、

環、啡

噻環、啡噻

環或啡環。苯環為最佳。 As the aromatic group, specifically, there can be mentioned a substituted or unsubstituted benzene ring, a naphthyl ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenyl ring, a perylene ring, a condensed pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring,

ring, triphenyl ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyridine ring, pyridine ring

Ring, pyrimidine ring,

Cyclic, indole

ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinone ring

Ring, quinoline ring, phthalide

Ring, naphthyridine ring, quinone

quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthroline ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring,

Ring, Coffee

Thiacinamide, phenthiophene

The benzene ring is the most preferred.

In addition, it is also preferred that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. There is no particular upper limit, but it is actually 50% by mass or less.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure can be copolymerized with the constituent unit represented by formula (1). Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be cited.

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

^A11 and ^A12 represent an oxygen atom or NH, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a free radical polymerizable group, and a free radical polymerizable group is preferred.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are independently defined as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), and the preferred ranges are also the same.

The definition of R ¹¹² is the same as that of R ¹¹² in formula (5), and the preferred range is also the same.

In the polyimide precursor, the repeated constituent units represented by formula (1) may be one type or two or more types. Furthermore, the structural isomers of the constituent units represented by formula (1) may be included. Furthermore, in addition to the constituent units of formula (1) above, the polyimide precursor may also include other types of constituent units.

As an embodiment of the polyimide precursor, a polyimide precursor can be exemplified in which 50 mol% or more, further 70 mol% or more, and especially 90 mol% or more of the total constituent units are constituent units represented by formula (1). As an upper limit, it is actually less than 100 mol%.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000~500000, more preferably 5000~100000, and further preferably 10000~50000. Moreover, the number average molecular weight (Mn) is preferably 800~250000, more preferably 2000~50000, and further preferably 4000~25000.

The molecular weight dispersion of the polyimide precursor is preferably 1.5~3.5, and 2~3 is even more preferred.

The polyimide precursor is a condensate of dicarboxylic acid or a dicarboxylic acid derivative and a diamine. It is preferably obtained by halogenating the dicarboxylic acid or the dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine.

In the method for producing a polyimide precursor, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more than one.

As the organic solvent, it can be appropriately set according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (DGE), N-methylpyrrolidone and N-ethylpyrrolidone.

When manufacturing a polyimide precursor, a process including solid precipitation is preferred. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation.

The proportion of the polyimide precursor in the film-forming composition is preferably 60% by mass or more of the components (solid components) other than the solvent, more preferably 70% by mass or more, and even more preferably 75% by mass or more, and preferably 99% by mass or less, and even more preferably 95% by mass or less.

The film-forming composition may contain only one polyimide precursor or two or more polyimide precursors. When two or more polyimide precursors are contained, it is preferred that the total amount be within the above range.

<<Solvent>>

The composition used in the film manufacturing method (film forming composition) contains at least two solvents having different solubility at 23°C relative to the polyimide precursor as solvents. Specifically, it is preferred to use a mixed solvent of at least solvent A having a higher solubility relative to the polyimide precursor and solvent B having a lower solubility at 23°C as solvents. The solubility is the amount (g) of the polyimide precursor dissolved in 100g of the solvent at 23°C.

When there are three or more solvents, the average of the solubility of the solvent with the highest solubility and the solubility of the solvent with the lowest solubility is calculated, and the solvent with a solubility higher than the average is classified as solvent A, and the solvent with a solubility lower than the average is classified as solvent B. Furthermore, when there are three or more solvents, it is preferred to set the solvent with the highest solubility as solvent A, and the solvent with the lowest solubility as solvent B.

The difference in solubility between solvent A and solvent B is preferably 10 g or more, more preferably 15 g or more, and even more preferably 20 g or more. There is no particular upper limit, and it can be set to 50 g or less, for example. With this structure, convection in the early stage of drying of the coating film can be further effectively suppressed.

The boiling point of solvent A is preferably above 100°C, more preferably above 110°C, and even more preferably above 130°C. The upper limit is preferably below 230°C, more preferably below 210°C, and even more preferably below 190°C. With this structure, the surface shape after coating tends to become more uniform.

The boiling point of solvent B is preferably above 150°C, more preferably above 180°C, and even more preferably above 200°C. The upper limit is preferably below 250°C, more preferably below 230°C, and even more preferably below 210°C. With this structure, the surface shape after coating tends to become more uniform.

It is preferred that solvent A and solvent B have a specified difference in boiling point. The difference in boiling point is preferably above 0°C, more preferably above 10°C, and even more preferably above 20°C. Furthermore, it is preferably below 80°C. With this structure, the surface shape can be kept uniform for a longer time compared to solvent B.

In addition, the boiling point in this manual refers to the temperature at which the liquid boils at 1013.25 hPa.

The solvent is preferably an organic solvent.

Examples of solvents classified as solvent A include sulfones, amides, and lactamides, among which sulfones are preferred.

As solvents classified as solvent B, esters, ethers, lactones, ketones, aromatic hydrocarbons, etc. can be cited, among which lactones or ketones are preferred, and ketones are more preferred.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, lactamides (γ-butyrolactone, ε-caprolactone, δ-valerolactone), alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example, 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester, etc. (for example, 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid ethyl ester)), 2-alkoxy-2-methyl propionic acid methyl ester and 2-alkoxy-2-methyl propionic acid ethyl ester (for example, 2-methoxy-2-methyl propionic acid methyl ester, 2-ethoxy-2-methyl propionic acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent 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. can be cited as preferred ones.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are preferably mentioned.

As aromatic hydrocarbons, for example, preferably toluene, xylene, anisole, limonene, etc. can be cited.

As the sulfoxides, for example, dimethyl sulfoxide can be cited as a preferred one.

As amides, preferred ones include lactamides (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone), N,N-dimethylacetamide, N,N-dimethylformamide, etc.

The content of the solvent is preferably set to an amount where the total solid content concentration of the film-forming composition is 1 to 80 mass %, more preferably 1 to 60 mass %, further preferably 5 to 40 mass %, and further preferably 5 to 35 mass %.

If the preferred ranges for each solvent are described, the content of solvent A (based on the total mass when there are multiple solvents) in the film-forming composition is preferably 1-80 mass%, more preferably 1-60 mass%, more preferably 5-40 mass%, and more preferably 5-30 mass%. The content of solvent B (based on the total mass when there are multiple solvents) in the film-forming composition is preferably 3-90 mass%, more preferably 6-80 mass%, more preferably 10-60 mass%, and more preferably 15-50 mass%.

The mass ratio of solvent A to solvent B (based on the total mass when there are multiple solvents) is preferably 10:90~45:55, more preferably 15:85~40:60, and even more preferably 20:80~30:70.

<<Surfactant>>

It is preferred that the film-forming composition contains a surfactant.

The above-mentioned surfactant is preferably a surfactant containing fluorine atoms, preferably a non-ionic or anionic surfactant containing fluorine atoms, and more preferably a non-ionic or anionic oligomer or polymer surfactant containing fluorine atoms. In addition, the surfactant preferably contains a perfluoroalkylene group, and more preferably contains a perfluoroalkylene group.

It is preferred that the surfactant is soluble in water. In this specification, soluble means that the solubility is 0.05 mass% or more at 23°C. Furthermore, it is preferred that the surfactant is soluble in water at 23°C at 0.1 mass% or more, more preferably at 0.5 mass% or more, and even more preferably at 1 mass% or more. The upper limit is actually 5 mass% or less.

The surfactant may have at least one of a hydrophilic group, a lipophilic group, and an ultraviolet-reactive group in the molecule.

Among them, in the present invention, from the perspective of improved moisture resistance, carboxylates (cationic system) containing perfluoroalkyl groups are preferred. The surfactant is preferably soluble in water or slightly soluble in water (for example, 0.1 mass % or more), but insoluble in hydrocarbon solvents (for example, hexane or toluene). The surface tension relative to a 0.1 mass % solution of water is preferably 10 mN/m or more, and 15 mN/m or more is more preferred. The upper limit is actually 50 mN/m or less. The surface tension relative to a 0.1% solution of PGME (propylene glycol monomethyl ether) is preferably greater than 25 mN/m, and 26 mN/m or more is more preferred. The upper limit is actually 70 mN/m or less.

As fluorine-based surfactants, specifically, there can be cited the trade names of Fluorinert F-C430 and Fluorinert F-C431 (both manufactured by Sumitomo 3M Limited); MEGAFACE F-142D, MEGAFACE F-171, MEGAFACE F-172, MEGAFACE F-173, MEGAFACE F-177, MEGAFACE F-183, MEGAFACE F-410, MEGAFACE F-444, MEGAFACE F-470, MEGAFACE F-471, MEGAFACE F-478, MEGAFACE F-479, MEGAFACE F-480, MEGAFACE F-482, MEGAFACE F-483, MEGAFACE F-484, MEGAFACE F-486, MEGAFACE F-487, MEGAFACE F-489, MEGAFACE F-553, MEGAFACE F-554, MEGAFACE F-556, MEGAFACE F-557, MEGAFACE F-569, MEGAFACE F-575, MEGAFACE F-780F, MEGAFACE F-781F, MEGAFACE R30 (all manufactured by DIC CORPORATION); F TOP EF301, F TOP EF303, F TOP EF351, F TOP EF352 (all manufactured by JEMCO Inc.); Surflon S381, Surflon S382, Surflon SC101, Surflon SC105 (all manufactured by ASAHI GLASS CO., LTD.); E5844 (DAIKIN INDUSTRIES, LTD.); BM-1000, BM-1100 (made by BM Chemie), etc.

Regarding the above-mentioned MEGAFACE series surfactants manufactured by DIC CORPORATION, the higher the hydrophilicity, the better, and the more fluorine atom content, the better. If the sequence of hydrophilicity is shown by a part of the object, it becomes F-410>F-444>F-430, F-510, F-511, F-569, F-553, F-477, F-556>>F-554. Regarding the fluorine atom content, it becomes F-430>F-410, F-510, F-511>F-444>>F-569, F-553, F-554, F-477, F-556. Regarding hydrophilicity and fluorine atom content, at least one of the left side of >> (more) is better, and the left side of >> (larger) is better among the two.

Regarding surfactants, MEGAFACE F-410 and F-444 (both trade names) showed good results in the adhesion test after PCT in the following examples. In contrast, F-510 and the like were inferior. From this point of view, MEGAFACE F-410 and F-444 are particularly good, and F-444 is even better.

The weight average molecular weight of the surfactant is preferably 30,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 4,000 or less. The lower limit is actually 500 or more.

Regarding the molecular weight of the surfactant, the method described in Example 1 of the embodiment of Japanese Patent Publication No. 2001-208736 was used. Specifically, ASAHIKLIN AK-225 SEC Grade 1 was used as the mobile phase, and two PL gel 5μm MIXED-E (inner diameter 7.5mm, length 30cm) manufactured by Polymer Laboratories Ltd. were connected in series as the SEC column. The mobile phase flow rate was set to 1.0ml per minute, the column temperature was set to 37°C, and a differential refractive index (RI) detector was used as the detector. The polarity was set to - for measurement.

The content of the surfactant in the solid content of the film-forming composition is preferably 0.0008 mass% or more, more preferably 0.005 mass% or more, and even more preferably 0.01 mass% or more. As the upper limit, 5 mass% or less is preferably, 4 mass% or less is more preferably, and 2 mass% or less is even more preferably. It can be 1 mass% or less, and can also be 0.5 mass% or less, 0.1 mass% or less, or 0.01 mass% or less.

Relative to the entire composition, 0.0001 mass% or more is preferred, 0.0005 mass% or more is more preferred, and 0.001 mass% or more is even more preferred. As the upper limit, 5 mass% or less is preferred, 2 mass% or less is even more preferred, and 1 mass% or less is even more preferred.

The content of the surfactant relative to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more. As the upper limit, 15 parts by mass or less is preferably, 10 parts by mass or less is more preferably, 5 parts by mass or less is even more preferably, 2 parts by mass or less is even more preferably, 1 part by mass or less is even more preferably, 0.5 parts by mass or less is even more preferably, and 0.1 parts by mass or less is even more preferably.

The surfactant may contain one or more than one. When containing two or more, it is preferred that the total amount be within the above range.

By adjusting the surfactant to the above range, the surface tension of the coating film of the film-forming composition can be reduced, the formation of the nanocells and their effects can be effectively suppressed, and the surface shape of the film can be further improved, so it is better.

<<Plasticizer>>

There is no particular limitation on the type of plasticizer used in the film-forming composition of the embodiment of the present invention, and a known plasticizer can be used.

Specifically, examples include phthalate, adipate, trimellitate, polyester, phosphate, citrate, epoxy plasticizer, sebacate, azelaic acid ester, maleic acid ester, and benzoate, with epoxy plasticizer being preferred.

Examples of epoxy plasticizers include epoxidized oils (epoxidized soybean oil, epoxidized linseed oil), epoxidized fatty acid alkyl (e.g., octyl) esters, etc.

As an epoxy plasticizer, an epoxy group having the following formula e1 or e2 in the molecule is preferred.

That is, the examples include those in which the formula e1 is introduced at the end or in the middle of the olefin chain or wax chain constituting the plasticizer, those in which the formula e2 is introduced in the middle of the chain, or those in which both of the above are introduced at the end and in the middle. The epoxy plasticizer is preferably a fatty acid or oil, and it is more preferable that a carboxyl group is introduced into the above olefin chain or wax chain. Among them, the carboxyl group can be partially or completely esterified by an alkyl group or the like. In the plasticizer, the carbon number is preferably 3 to 48, more preferably 4 to 36, and even more preferably 6 to 24.

Specifically, O-180A, O-130P, D-32, and D-55 (all trade names) manufactured by ADEKA CORPORATION can be cited, among which O-180A, O-130P, and D-32 are preferred.

The viscosity of the plasticizer at 25°C is preferably 40mPa.s or more, more preferably 100mPa.s or more, and even more preferably 200mPa.s or more. The upper limit is actually 800mPa.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 it is actually 9.5 or less.

The content of the plasticizer in the solid content of the film-forming composition is preferably 0.0008 mass% or more, more preferably 0.005 mass% or more, and even more preferably 0.01 mass% or more. As the upper limit, 5 mass% or less is preferably, 4 mass% or less is more preferably, and 2 mass% or less is even more preferably. It can be 1 mass% or less, and can also be 0.5 mass% or less, 0.1 mass% or less, or 0.01 mass% or less.

The content of the plasticizer relative to 100 parts by mass of the polyimide precursor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more. As the upper limit, 15 parts by mass or less is preferably, 10 parts by mass or less is more preferably, 5 parts by mass or less is even more preferably, 2 parts by mass or less is even more preferably, 1 part by mass or less is even more preferably, 0.5 parts by mass or less is even more preferably, and 0.1 parts by mass or less is even more preferably.

The plasticizer may contain one type or two or more types. When two or more types are contained, it is preferred that the total amount be within the above range.

By setting the plasticizer to the above range, it is better to prevent the film surface from drying up, avoid the continuous formation of nanocells, and obtain a better surface shape of the coating film.

<<Photopolymerization initiator>>

The film-forming composition may contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.

There is no particular limitation on the photoradical polymerization initiator that can be used in the present invention, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, an activator that can react with a photoexcited sensitizer to generate active radicals can be used.

The photo-radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300-800 nm (preferably 330-500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and using an ethyl acetate solvent at a concentration of 0.01 g/L.

骨架之化合物、具有

二唑骨架之化合物、具有三鹵甲基之化合物等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等的詳細內容，能夠參閱日本特開2016-027357號公報的0165~0182段的記載，並將該內容編入本說明書中。 As the photoradical polymerization initiator, any known compound can be used, and examples thereof include halogenated hydrocarbon derivatives (e.g., having three

Skeleton compounds, having

Compounds having a triazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. For details of the above, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357, and the contents are incorporated into this specification.

As ketone compounds, for example, compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611 can be exemplified, and the contents are incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photo-radical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Publication 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 such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As aminoacetophenone-based initiators, compounds described in Japanese Patent Publication No. 2009-191179, which have a maximum absorption wavelength that matches a wavelength light source such as 365nm or 405nm, can also be used.

As the acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and the like can be cited. In addition, commercially available products such as IRGACURE-819 or IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784 (manufactured by BASF Corporation) and the like.

As a photo-radical polymerization initiator, an oxime compound is more preferred. By using an oxime compound, the exposure tolerance can be further effectively improved. Among oxime compounds, the exposure tolerance (exposure margin) is wider and it also functions as a photocuring accelerator, so it is particularly preferred.

As specific examples of oxime compounds, compounds described in Japanese Patent Publication No. 2001-233842, compounds described in Japanese Patent Publication No. 2000-080068, and compounds described in Japanese Patent Publication No. 2006-342166 can be used.

As a preferred oxime compound, reference can be made to paragraphs 0080 to 0083 of Japanese Patent Publication No. 2015-189883, and such contents are incorporated into this specification.

化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基

二唑化合物、3-芳基取代香豆素化合物之群 組中之化合物。 From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is selected from the group consisting of trihalomethyl tri

compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halogenated methyl

A compound from the group consisting of oxadiazole compounds and 3-aryl substituted coumarin compounds.

In addition, the photo-radical polymerization initiator can also use the compounds described in paragraphs 0048 to 0055 of the international publication WO2015/125469.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass % relative to the total solid content of the film-forming composition, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass %. The photopolymerization initiator may contain only one or more. When two or more photopolymerization initiators are contained, it is preferred that the total is within the above range.

<<Thermal free radical polymerization initiator>>

The film-forming composition may contain a thermal radical polymerization initiator.

Thermal radical polymerization initiators are compounds that generate free radicals by heat energy and start or promote the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, cyclization of polyimide precursors can be performed and polymerization of polyimide precursors can be performed, thereby achieving a higher degree of heat resistance.

As thermal radical polymerization initiators, specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited.

When a thermal free radical polymerization initiator is contained, its content is preferably 0.1 to 30 mass % relative to the total solid content of the film-forming composition, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass %. The thermal free radical polymerization initiator may contain only one or more. When two or more thermal free radical polymerization initiators are contained, their total is preferably within the above range.

<<Polymerizable compounds>>

<<<Free Radical Polymerization Compounds>>>

It is preferred that the film-forming composition contains a free radical polymerizable compound.

The free radical polymerizable compound can use a compound having a free radical polymerizable group. As the free radical polymerizable group, there can be cited groups having ethylenic unsaturated bonds such as vinylphenyl, vinyl, (meth)acryl and allyl. The free radical polymerizable group is preferably (meth)acryl.

The number of free radical polymerizable groups possessed by the free radical polymerizable compound may be 1 or more than 2. It is preferred that the free radical polymerizable compound possesses more than 2 free radical polymerizable groups, and more preferably possesses more than 3 free radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

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

From the perspective of developing properties, it is preferred that the film-forming composition contains at least one radically polymerizable compound having two or more functional groups, and it is more preferred that it contains at least one radically polymerizable compound having three or more functional groups. In addition, it may be a mixture of a radically polymerizable compound having two or more functional groups and a radically polymerizable compound having three or more functional groups. In addition, the number of functional groups of a radically polymerizable compound refers to the number of radically polymerizable groups in one molecule.

Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, and hydroxyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and alcohols, and substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and alcohols are also preferred. Moreover, as another example, instead of the above-mentioned unsaturated carboxylic acids, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and such contents are incorporated into this specification.

In addition, the radical polymerizable compound is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipentylthritol penta(meth)acrylate, dipentylthritol hexa(meth)acrylate, hexylene glycol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are (meth)acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol. Compounds described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, polyfunctional acrylates or methacrylates such as epoxy acrylates as reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be cited.

Furthermore, as a preferred free radical polymerizable compound other than the above, a compound having a fluorene ring and having two or more groups containing ethylenic unsaturated bonds or a cardo resin described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc. can also be used.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application No. 2015-034964 can also be preferably used, and such contents are incorporated into this specification.

In addition, the following compounds described in Japanese Patent Publication No. 10-062986 as formula (1) and formula (2) together with their specific examples can also be used as free radical polymerizable compounds. The compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylic acid esterification.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application No. 2015-187211 can also be used as other free radical polymerizable compounds, and such contents are incorporated into this specification.

As the radical polymerizable compound, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. Such oligomer types can also be used.

As commercially available free radical polymerizable compounds, for example, there can be cited SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc. as a bifunctional methyl acrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentoxy chains, TPA-330 as a trifunctional acrylate having three isobutyloxy chains, urethane oligomer UAS-10, urethane oligomer UAB-140 (NIPPON PAPER INDUSTRIES CO.,LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin-Nakamura Chemical Co.,Ltd.), DPHA-40H (Nippon Kayaku Co.,Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co.,Ltd.), BLEMMER PME400 (NOF CORPORATION.), etc.

As free radical polymerizable compounds, urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those 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 preferred. Furthermore, as free radical polymerizable compounds, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

The free radical polymerizable compound may be a free radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical polymerizable compounds having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. Particularly preferred is a free radical polymerizable compound having an acid group by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides, wherein the aliphatic polyhydroxy compound is a compound of neopentyl triol and/or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510 and M-520.

The preferred acid value of the radical polymerizable compound having an acid group is 0.1~40 mgKOH/g, and the most preferred acid value is 5~30 mgKOH/g. As long as the acid value of the radical polymerizable compound is within the above range, the manufacturing or handling properties are excellent, and further the developing properties are excellent. In addition, the polymerizability is also good.

As the radical polymerizable compound, a monofunctional radical polymerizable compound can be preferably used. As the monofunctional radical polymerizable compound, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical polymerizable compound, in order to suppress volatility before exposure, a compound having a boiling point of 100°C or above at normal pressure is also preferred.

<<<Polymerizable compounds other than the above-mentioned free radical polymerizable compounds>>>

化合物。 The film-forming composition may further contain polymerizable compounds other than the above-mentioned radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; cyclohexane compounds; benzophenone compounds;

Compound.

(Compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl groups)

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 preferred.

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

(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 , R ⁴⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, 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, 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 (these are trade names, manufactured by ASAHI YUKIZAI CORPORATION), 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 (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol), etc.

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

(Epoxy compounds (compounds with epoxy groups))

As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C, and since it does not induce a dehydration reaction originating from the crosslinking, it is difficult to cause film shrinkage. Therefore, by containing an epoxy compound, the low-temperature curing of the composition and the warping of the film can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. 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 epoxy resin, bisphenol F epoxy resin, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EPICLON (registered trademark) EXA-859CRP (trade name, manufactured by DIC Corporation), EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (these are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (these are trade names, manufactured by ADEKA CORPORATION), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred from the perspective of suppressing warping and having excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA- 4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

(Oxycyclobutane compounds (compounds with oxycyclobutyl groups))

As cyclooxobutane compounds, compounds having two or more cyclooxobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-cyclooxobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)cyclooxobutane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-cyclooxobutyl)methyl]ester, etc. can be cited. As a specific example, ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

化合物(具有聚苯并

唑基之化合物)) (Benzo

Compound (with polyphenylene

Azolyl compounds

化合物因源自開環加成反應之交聯反應而於硬化時不產生脫氣，進而減少熱收縮而抑制產生翹曲，因此為較佳。 Benzo

The compound is preferred because it does not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and suppressing the generation of warp.

化合物的較佳的例，可舉出B-a型苯并

、B-m型苯并

(以上為商品名，Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并

加成物、酚醛清漆型二氫苯并

化合物。該等可以單獨使用，或者可以混合兩種以上。 As benzo

Preferred examples of compounds include Ba-type benzo

、Bm type benzo

(the above are trade names, manufactured by Shikoku Chemicals Corporation), benzophenone

Adduct, novolac type dihydrobenzo

These may be used alone or in combination of two or more.

When a polymerizable compound is contained, its content relative to the total solid content of the film-forming composition is preferably greater than 0 mass % and less than 60 mass %. The lower limit is more preferably 5 mass %. The upper limit is more preferably 50 mass % or less, and more preferably 30 mass % or less.

The polymerizable compound can be used alone or in combination of two or more. When two or more are used simultaneously, it is preferred that the total amount be within the above range.

<<Migration inhibitor>>

It is preferred that the film-forming composition further includes a migration inhibitor. By including a migration inhibitor, it is possible to effectively inhibit metal ions from the metal layer (metal wiring) from migrating into the film of the film-forming composition.

唑環、噻唑環、吡唑環、異

唑環、異噻唑環、四唑環、吡啶環、噠

環、嘧啶環、吡

環、哌啶環、哌

環、

啉環、2H-吡喃環及6H-吡喃環、三

環)之化合物、具有硫脲類及巰基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。 The migration inhibitor is not particularly limited, and examples thereof include those having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole, thiazole, pyrazole, iso

Azole ring, isothiazole ring, tetrazole ring, pyridine ring,

Ring, pyrimidine ring, pyridine

Ring, piperidine ring, piperidine

Ring,

Phylindole, 2H-pyrandole, 6H-pyrandole, tri

Compounds having a thiourea group and a hydroxyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

In addition, an ion capture agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, and the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Publication No. 2012-194520 can be used.

As specific examples of migration inhibitors, the following compounds can be cited.

[Chemistry 16]

When the film-forming composition contains a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the film-forming composition is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %.

There can be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is better for their total to be within the above range.

<<Polymerization inhibitor>>

It is preferred that the film-forming composition contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, oligol, p-tert-butyl-o-catechol, 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-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenyl Naphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO2015/125469 can also be used.

In addition, the following compounds (Me is methyl) can also be used.

When the film-forming composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass % relative to the total solid content of the film-forming composition.

The polymerization inhibitor may be only one or two or more. When there are two or more polymerization inhibitors, it is preferred that the total amount is within the above range.

<Metal adhesion improver>

The film-forming composition preferably includes a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of the metal adhesion improver include silane coupling agents, etc.

Examples of silane coupling agents include compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

In addition, the metal adhesion improver can also use the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfides described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935.

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 0.5 to 5 parts by mass relative to 100 parts by mass of the polyimide precursor. By setting it above the lower limit, the adhesion between the film and the metal layer after the curing process becomes good, and by setting it below the upper limit, the heat resistance and mechanical properties of the film after the curing process become good. The metal adhesion improver can be only one or more than two. When two or more are used, it is better for the total to be in the above range.

<Hardening accelerator>

The film-forming composition may contain a curing accelerator. The curing accelerator may be a thermal curing accelerator or a photocuring accelerator.

<<Thermal curing accelerator>>

The heat curing accelerator is preferably one that generates a base by heating. The preferred range of the heating temperature (base generation temperature) is the same as the temperature specified in the heating process described below. The salt of a tertiary amine or a quaternary ammonium cation and a carboxylic acid anion is preferred. The tertiary amine and the quaternary ammonium cation are preferably represented by any one of the following formulas (Y1-1) to (Y1-4).

R ^Y1 represents an organic group with a valence of ^nY ( ^nY is an integer of 1 to 12), preferably a alkyl group. Examples of the alkyl group include groups containing alkanes (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), groups containing alkenes (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), groups containing aromatic hydrocarbons (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or combinations thereof. Among these, ^{R Y1} is preferably an aromatic hydrocarbon group. Within the range not impairing the effects of the present invention, ^RY1 may have a substituent T (hydroxyl group, carboxyl group, amino group (NR ^N ₂ ), alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), acyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aminoformyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms, ^RN is a hydrogen atom or a group having the same definition as the group represented by ^RY2 ).

^RY2 to ^RY5 each independently represent a hydrogen atom or a alkyl group (preferably having 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, and further preferably 1 to 12 carbon atoms), an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, and further preferably 1 to 23 carbon atoms), an alkenyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and further preferably 2 to 23 carbon atoms), an alkynyl group (preferably having 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, and further preferably 1 to 23 carbon atoms), or an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).

^RY6 is alkyl (preferably having 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and more preferably 4 to 18 carbon atoms), alkenyl (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and more preferably 4 to 18 carbon atoms), alkynyl (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and more preferably 4 to 18 carbon atoms), or aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms).

n ^Y represents an integer from 1 to 12, an integer from 1 to 6 is preferred, and an integer from 1 to 3 is further preferred.

n ^X represents an integer from 1 to 12, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

In ^RY2 to ^RY6 , the alkyl, alkenyl, and alkynyl groups may be cyclic or chain-shaped. When they are chain-shaped, they may be straight or branched. In the alkyl, alkenyl, alkynyl, and aryl groups, a linking group L (carbonyl, oxygen atom, sulfur atom, NR ^N , alkylene (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenylene (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), arylene (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms) or a combination of these linking groups may be present between the groups or in the connection with the parent nucleus.

Two or more of ^RY2 to ^RY6 can be bonded to each other to form a ring.

^RY2 to ^RY6 may have a substituent T.

R ^Y7 to R ^Y16 are hydrogen atoms or substituents. Not all of R ^Y7 to R ^Y9 are hydrogen atoms. The substituent is preferably an organic group (preferably having 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, and even more preferably 1 to 12 carbon atoms), sometimes interposed with a linking group L, and preferably a alkyl group having a substituent T. As the alkyl group, the group of R ^Y2 is preferred.

In formula (Y1-2), ^RY7 and ^RY8 are preferably carboxyalkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms; the number of carboxyl groups is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms). ^RY9 is preferably an aromatic group, preferably an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms). Alternatively, it is preferably an alkoxycarbonyl group substituted with an aromatic group (the number of carbon atoms of the alkoxy group is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms; the number of carbon atoms of the aromatic group is preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 14 carbon atoms).

Another preferred embodiment of formula (Y1-2) is that ^RY7 and ^RY8 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms). ^RY9 is preferably a group having an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), and preferably an alkoxycarbonyl group having an aromatic group.

In formula (Y1-3), R ^Y11 and R ^Y13 are preferably hydrogen atoms. R ^Y14 and R ^Y15 may be combined to form a substituent of the form =C(NR ^N ₂ ) ₂ (= means double bond and bonded to the nitrogen atom).

In formula (Y1-4), ^RY13 is preferably a hydrogen atom, and ^RY10 , ^RY11 , ^RY12 , and ^RY16 are preferably alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms). In this case, ^RY11 and ^RY16 , and ^RY10 and ^RY12 are preferably bonded to form a ring and a bicyclic compound is preferably formed. Specifically, diazabicyclononene and diazabicycloundecene are exemplified.

In this embodiment, the carboxylic acid anion that pairs with the quaternary ammonium cations of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is preferably represented by the following formula (X1).

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

In this embodiment, the electron-withdrawing group refers to a group whose Hammett substituent constant σm represents a positive value. σm is described in detail in Yufu Mitsuno's Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in this embodiment is not limited to the substituents described in the above literature.

Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group (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), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same).

EWG is preferably a group represented by the following formula (EWG-1)~(EWG-6).

In formula (EWG-1) to (EWG-6), ^Rx1 to ^Rx3 independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), a hydroxyl group, or a carboxyl group. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms). When ^Rx1 to ^Rx3 are alkyl groups, alkenyl groups, or aryl groups, a ring may be formed. The alkyl groups, alkenyl groups, aryl groups, and Ar may have a substituent T within the scope of not impairing the effects of the present invention. Among them, Ar preferably has a carboxyl group (preferably 1 to 3). * indicates a bonding position.

^L1 is defined the same as the linking group L, and is ^-CRX2RX3- , ^-Ar1- , or a group formed by combining these. ^Ar1 is an aryl group (preferably having 6 to ²² carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms).

Np represents an integer from 1 to 6, preferably an integer from 1 to 3, and more preferably 1 or 2.

The molecular weight of the thermosetting accelerator is preferably greater than 100 and less than 2000, and more preferably 200-1000.

As specific examples of thermal curing accelerators, acidic compounds that generate bases when heated to above 40°C and ammonium salts with a pKa1 of 0 to 4 and having anions and ammonium cations are exemplified in International Publication No. 2015/199219, and these contents are incorporated into this specification.

When a thermosetting accelerator is used, the content of the thermosetting accelerator in the composition is preferably 0.01 to 50 mass % relative to the total solid content of the composition. The lower limit is preferably 0.05 mass % or more, and 0.1 mass % or more is further preferred. The upper limit is preferably 10 mass % or less, and 5 mass % or less is further preferred.

One or more thermosetting accelerators can be used. When two or more are used, the total amount is preferably within the above range. In addition, the film-forming composition can be configured to substantially not contain a thermosetting accelerator. Substantially not containing means that the amount is less than 0.01% by mass, and preferably less than 0.005% by mass, relative to the total solid content of the composition.

<<Photohardening accelerator>>

The film-forming composition may contain a photocuring accelerator. The photocuring accelerator is preferably one that generates a base by exposure. It is not active under normal conditions of room temperature and pressure, but is preferably one that generates a base (alkaline substance) when electromagnetic waves are irradiated and heated as external stimuli. The base generated by exposure acts as a catalyst when the polyimide precursor is heated to cure, so it can be used preferably. The preferred conditions for exposure are the same as those specified in the exposure process described below.

As the photocuring accelerator, known ones can be used. For example, there can be cited metal transfer compound complexes, those having structures such as ammonium salts, ionic compounds in which the base component is neutralized by forming salts such as those in which the amidine part is latently oxidized by forming salts with carboxylic acids, carbamate derivatives, oxime ester derivatives, acyl compounds, and other non-ionic compounds in which the base component is latently oxidized by carbamate bonds or oxime bonds.

As the photocuring accelerator, for example, there can be cited a photocuring accelerator having a cinnamic acid amide structure as disclosed in Japanese Patent Publication No. 2009-080452 and International Publication No. 2009/123122, a photocuring accelerator having a carbamate structure as disclosed in Japanese Patent Publication No. 2006-189591 and Japanese Patent Publication No. 2008-247747, and a photocuring accelerator having an oxime structure or a carbamoyl oxime structure as disclosed in Japanese Patent Publication No. 2007-249013 and Japanese Patent Publication No. 2008-003581, but the present invention is not limited to these, and other known photocuring accelerator structures can also be used.

In addition, as photohardening accelerators, compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of Japanese Patent Publication No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese Patent Publication No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese Patent Publication No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010/064631 can be cited as examples.

As commercially available products of photohardening accelerators, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-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 mass % relative to the total solid content of the composition. The lower limit is preferably 0.5 mass % or more, and 1 mass % or more is further preferred. The upper limit is preferably 30 mass % or less, and 20 mass % or less is further preferred.

One or more photohardening accelerators can be used. When two or more are used, the total amount is preferably within the above range.

<Other additives>

The film-forming composition can be compounded with various additives as needed, such as thermal acid generators, sensitizing pigments, chain transfer agents, surfactants other than the above, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, and aggregation inhibitors, within the scope of not damaging the effects of the present invention. When compounding such additives, it is preferred that the total compounding amount is set to 3% by weight or less of the solid content of the composition.

<<Thermal Acid Generator>>

The film-forming composition may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the polyimide precursor to further improve the mechanical properties of the film. As for the thermal acid generator, the compounds described in paragraph 0059 of Japanese Patent Publication No. 2013-167742 can be cited. The preferred range of the heating temperature (acid generation temperature) of the thermal acid generator is the same as the temperature specified in the heating process described later.

The content of the thermal acid generator is preferably 0.01 parts by mass or more relative to 100 parts by mass of the polyimide precursor, and 0.1 parts by mass or more is more preferred. The thermal acid generator contains 0.01 parts by mass or more to promote the crosslinking reaction and the cyclization of the polyimide precursor, thereby further improving the mechanical properties and chemical resistance of the membrane. In addition, from the perspective of the electrical insulation of the membrane, the content of the thermal acid generator is preferably 20 parts by mass or less, 15 parts by mass or less is more preferred, and 10 parts by mass or less is even more preferred.

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

<<Sensitizing pigment>>

The film-forming composition may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. For details about the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, and the contents are incorporated into this specification.

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

<<Chain transfer agent>>

唑類、3-巰基三唑類、5-巰基四唑類等)。 The film-forming composition may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonating after oxidation. In particular, thiol compounds (for example, 2-benzimidazoles ...

azoles, 3-pentyltriazoles, 5-pentyltetrazoles, etc.).

When the film-forming composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the film-forming composition. The chain transfer agent may be only one or more than two. When there are more than two chain transfer agents, it is preferred that the total is within the above range.

<<Higher fatty acid derivatives>>

In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the film-forming composition and locally exist on the surface of the composition during the drying process after coating.

When the film-forming composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the film-forming composition. The higher fatty acid derivative may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably within the above range.

<Regarding restrictions on other substances>

From the perspective of the coating surface, the water content of the film-forming composition is preferably less than 5 mass %, more preferably less than 1 mass %, and even more preferably less than 0.6 mass %.

From the perspective of insulation, the metal content of the film-forming composition is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are included, the total of the metals is preferably within the above range.

In addition, as a method for reducing metal impurities accidentally contained in the film-forming composition, it is possible to cite methods such as selecting a raw material with a low metal content as a raw material constituting the film-forming composition, filtering the raw material constituting the film-forming composition with a filter, lining the inside of the device with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.

From the perspective of wiring corrosion, the content of halogen atoms in the film-forming composition is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the content of halogen atoms in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is respectively within the above range.

As a container for storing the film-forming composition, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the composition, it is also preferable to use a multi-layer bottle with six layers of six resins forming the inner wall of the container, or a bottle with six resins forming a seven-layer structure. As such containers, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Preparation of composition>

The film-forming composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as garbage or particles in the composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a cycle filtration. In addition, filtering can be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurization is preferably greater than 0.05MPa and less than 0.3MPa.

In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

<Each process>

The manufacturing method of the present invention preferably has an exposure process for exposing and a development process for developing the exposed film after the film forming process. After the development, the exposed film can be further hardened by heating.

When forming a laminated body, according to the manufacturing method of the above-mentioned cured film, after forming the film, it is preferable to sequentially perform the film forming process and heating process, film forming process, exposure process and development process (and further perform the heating process as needed). In particular, it is preferable to sequentially perform each of the above processes multiple times (preferably 2 to 5 times, that is, 3 to 6 times in total). By laminating the film in this way, a laminated body with the desired number of layers can be formed. When forming the laminated body, it is preferable to apply a metal layer.

<<Film formation process>>

In the manufacturing method of the present invention, as described above, it is preferred that the film forming process includes applying the film forming composition to a substrate to form a film.

The type of substrate can be appropriately set according to the purpose, but is not particularly limited to semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, evaporated film, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, plasma display panel (PDP) electrode plate, etc. Among them, in the present invention, the substrate is a component that contains metal in at least a part (for example, a substrate provided with a metal layer). In the present invention, the surface shape of the above-mentioned resin film can be well formed by slit coating the film-forming composition on the metal surface. In addition, the shape of the substrate is preferably quadrilateral, and more preferably rectangular.

In the film manufacturing method of the present invention, it is preferable to use a slit coater as a method of applying the film-forming composition to the substrate.

The slit width of the nozzle is preferably 20μm or more, more preferably 50μm or more, and more preferably 80μm or more. As the upper limit, it is preferably 250μm or less, more preferably 200μm or less, and more preferably 150μm or less.

The slit gap is preferably 30μm or more, more preferably 50μm or more, and even more preferably 70μm or more. As the upper limit, it is preferably 200μm or less, more preferably 150μm or less, and even more preferably 120μm or less.

The scanning speed can be above 1mm/s, preferably above 10mm/s, more preferably above 20mm/s, and more preferably above 30mm/s. As the upper limit, preferably below 500mm/s, more preferably below 400mm/s, and more preferably below 300mm/s.

The coating film thickness is preferably 1μm or more, more preferably 2μm or more, and even more preferably 3μm or more. As the upper limit, 100μm or less is preferably, 80μm or less is more preferably, and 50μm or less is even more preferably.

<<Drying process>>

The manufacturing method of the present invention may also include a drying process to remove the solvent after the film is formed. The preferred drying temperature is 50-150°C, 70-130°C is more preferred, and 90-110°C is further preferred. The drying time is exemplified as 30 seconds to 20 minutes, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

The thickness of the dried film can be set to, for example, 0.5 μm or more, or 1 μm or more. Also, as an upper limit, it can be set to 100 μm or less, or 30 μm or less. This thickness is also the same as the film thickness after the heating process described later.

<<Exposure process>>

Regarding the exposure amount in the exposure process, for example, based on the exposure energy at a wavelength of 365nm, it is better to irradiate 100~10000mJ/ ^cm2 , and it is more better to irradiate 200~8000mJ/ ^cm2 .

The exposure wavelength can be appropriately set within the range of 190~1000nm, with 240~550nm being the best.

Regarding the exposure wavelength, if described in terms of its relationship with the light source, the following examples are mentioned: (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), and (6) electron beams. Regarding the film-forming composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

<<Developing process>>

Regarding the developing method in the developing process, there is no particular limitation as long as the desired pattern can be formed. For example, developing methods such as rotary immersion, spraying, immersion, and ultrasonic waves can be used.

The development is preferably performed using a developer. As long as the developer can remove the unexposed part (non-exposed part), it can be used without special restrictions. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula into ChemBioDraw.

As for the organic solvent, examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.) ), 3-alkoxy propionic acid alkyl esters (e.g., 3-alkoxy propionic acid methyl ester, 3-alkoxy propionic acid ethyl ester, etc. (e.g., 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (e.g., 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester, etc. (e.g., 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid methyl ester, ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl Solvent 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., and 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, etc., and as sulfoxides, dimethyl sulfoxide can be preferably exemplified.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is even more preferred.

It is preferred that more than 50% by mass of the developer is an organic solvent, more preferably more than 70% by mass is an organic solvent, and even more preferably more than 90% by mass is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

The best development time is 10 seconds to 5 minutes. There is no specific limit on the temperature during development, but it can usually be done at 20 to 40°C.

After the developer is used for treatment, rinsing can be performed. It is preferred that the rinsing be performed with a solvent different from the developer. For example, the solvent contained in the film-forming composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

<<Heating process>>

During the heating process, the cyclization reaction of the polyimide precursor is carried out. As the heating temperature (maximum heating temperature) in the heating process, 50~500℃ is preferred, 80~450℃ is more preferred, 140~400℃ is further preferred, and 160~350℃ is further preferred.

Regarding heating, it is preferred to heat from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 2°C/min or more, it is possible to ensure productivity while preventing excessive amine volatilization, and by setting the heating rate to 12°C/min or less, it is possible to alleviate the residual stress of the membrane.

The temperature at the start of heating is preferably 20℃~150℃, more preferably 20℃~130℃, and even more preferably 25℃~120℃. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the film-forming composition is applied to the substrate and then dried, it is the temperature after drying. For example, it is better to gradually increase the temperature from a temperature 30~200℃ lower than the boiling point of the solvent contained in the film-forming composition.

The heating time (heating time at the highest 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-layer laminate, from the perspective of the adhesion between the layers of the film, it is better to heat at a heating temperature of 180℃~320℃, and it is more preferably heated at 180℃~260℃. Although the reason is uncertain, it is believed that the reason is as follows, that is, by setting the temperature to this level, the acetylene groups of the polyimide precursor between the layers undergo cross-linking reactions.

Heating can be performed in stages. For example, the pre-treatment process can be performed by heating from 25°C to 180°C at 3°C/min and maintaining at 180°C for 60 minutes, and then heating from 180°C to 200°C at 2°C/min and maintaining at 200°C for 120 minutes. The heating temperature of the pre-treatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pre-treatment process, it is also preferred to perform the treatment while irradiating with ultraviolet rays as described in the specification of U.S. Patent No. 9159547. The properties of the membrane can be improved by such pre-treatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is better. The pretreatment can be a process of more than two stages, for example, pretreatment process 1 can be carried out in the range of 100~150℃, and then pretreatment process 2 can be carried out in the range of 150~200℃.

Furthermore, cooling can be performed after heating, and the cooling speed in this case is preferably 1~5℃/minute.

Regarding the heating process, from the perspective of preventing the decomposition of the polyimide precursor, it is better to carry out the process in an environment with low oxygen concentration by flowing inert gases such as nitrogen, helium, and argon. The oxygen concentration is preferably below 50ppm (volume ratio), and more preferably below 20ppm (volume ratio).

<<Metal layer formation process>>

A metal layer can be applied to the surface of the film-forming composition after development.

As the metal layer, there is no particular limitation, and existing metal types can be used, examples of which include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.1~50μm at the thickest wall, and more preferably 1~10μm.

<<Layering process>>

The lamination process may include sequentially performing the above-mentioned film formation process and heating process or the film formation process, the above-mentioned exposure process and the above-mentioned development process again on the surface of the film or metal layer of the film formation composition. The lamination process may also include the above-mentioned drying process or heating process, etc.

When a further layering process is performed after the layering process, a surface activation process may be performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer forming process. Plasma treatment is exemplified as the surface activation process.

The above-mentioned lamination process is preferably performed 2 to 5 times, and 3 to 5 times is even more preferred.

For example, a structure of 3 or more resin layers and 7 or less resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferred, and 3 or more layers and 5 or less layers is further preferred.

That is, after the metal layer is provided, the film forming process and the heating process of the film forming composition are sequentially performed in a manner covering the metal layer, or the film forming process, the exposure process and the developing process are sequentially performed on the film forming composition (and the heating process is further performed as needed). By alternately performing the film (resin) lamination process of the film forming composition and the metal film formation process, the film (resin layer) of the film forming composition and the metal layer can be alternately laminated.

As a specific example of a semiconductor device in which a film of a film-forming composition obtained by the manufacturing method of the present invention is used in the formation of an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, and such contents are incorporated into this specification.

The present invention also discloses a method for manufacturing a semiconductor device of a film-configured chip of the present invention. Furthermore, the present invention discloses a method for manufacturing a semiconductor device of a multilayer-configured chip. For the chip and chip configuration method here, please refer to the description of "Three-dimensional practical mounting technology of semiconductors", Seiichi Denda, CQ Publishing Co., Ltd., published on June 1, 2011, and the contents are incorporated into this manual.

[Implementation example]

The following examples are given to further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing processes, etc. shown in the following examples can be appropriately changed within the scope of the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

<Synthesis Example 1>

[Synthesis of polyimide precursor resin A-1 derived from pyromellitic anhydride, 4,4'-diaminodiphenyl ether and 3-hydroxybenzyl alcohol]

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were suspended in 50 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was heated at 100°C for 3 hours. A transparent solution was obtained after several minutes of heating. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of sulfinyl chloride was added over 10 minutes while the temperature was maintained at -10±4°C. During the addition of thionyl chloride, the viscosity increased. After dilution 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 20-23°C over 20 minutes. Then, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide protopolymer resin was precipitated in 5 liters of water, and the water-polyimide protopolymer resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. The polyimide precursor had Mw=22800 and Mn=8100.

<Synthesis Example 2>

[Synthesis of polyimide precursor resin A-2 derived from oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat bottom joint equipped with a stirrer, a condenser and an internal thermometer, 20.0 g (64.5 mmol) of oxydiphthalic anhydride was suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added successively, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent liquid. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Next, 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. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. The polyimide precursor had Mw=23500 and Mn=8800.

<Synthesis Example 3>

[Synthesis of polyimide precursor resin A-3 derived from oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat bottom joint equipped with a stirrer, a condenser and an internal thermometer, 10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 9.47 g (32.3 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added successively, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. 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. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. In the polyimide precursor, Mw=24300, Mn=9500.

<Preparation of film-forming composition>

The membrane-forming compositions of each embodiment and comparative example were prepared as a uniform solution mixed in the ratio (mass fraction) shown in the following table. In the examples described below, the obtained compositions were filtered with a polyethylene filter having a pore size of 0.8 μm and used.

<Film formation by slit coating>

As a substrate, a substrate on which a copper film with a thickness of 100 nm was produced by sputtering on the surface of an alkaline-free glass substrate with a width of 150 mm, a length of 150 mm, and a thickness of 0.7 mm was prepared. On the surface of the substrate, a coating film of the film-forming composition prepared above was formed using a slit coater (SCREEN FINETECH SOLUTIONS CO., LTD., LC-R300G, wherein the slit head width was set to 100 mm and the coating length was set to 100 mm). The detailed conditions of the slit coater are shown in the table below. After being placed at 23°C and reduced pressure of 50Pa for 5 minutes, it was dried on a heating plate at 100°C for 5 minutes. The coating film thickness (after drying) was measured at 10mm intervals from the end of the coating part to a position of 10mm using the F20 film thickness measuring system manufactured by Filmetrics Japan, Inc., and the average value was calculated. During film formation, the nozzle head was immersed in the immersion liquid under the conditions shown in the following table during the nozzle standby process. In addition, after film formation, the nozzle head was immersed in the cleaning liquid during the nozzle cleaning process. The temperature during immersion and cleaning was set to (normal temperature (23°C)).

<Paintability>

The coating properties of the above-mentioned narrow slit coating were evaluated. The coating film formed on the substrate was placed at 23°C and reduced pressure of 50Pa for 5 minutes, and then dried on a heating plate at 100°C for 5 minutes. It was then observed with the naked eye to confirm whether extrusion or streaks were observed. The observation area was the entire surface except for the end surface of the coating part to 10mm. In each embodiment and comparative example, the average value of 3 samples was adopted.

Little or no crowding or streaking, and uniform: Excellent

Some crowding or streaking found but generally uniform: Good

More crowding or stripes: below standard

<Surface shape after coating and drying>

The surface shape of the coating after drying in the above-mentioned narrow slit coating was evaluated. The coating film (after drying) formed on the substrate was observed with the naked eye, and the surface shape was confirmed from the reflection state of the fluorescent lamp. In each embodiment and comparative example, the average value of 3 samples was adopted.

Direct specular reflection of fluorescent light in the entire coating area - Gloss: Excellent

There is a fluorescent blur in at least a part of the coating - weak orange peel: good

Fluorescent blur on the entire surface of the applied area - Orange peel: Below standard

<Surface uniformity after coating and drying>

The in-plane uniformity of the coating thickness after drying during the above-mentioned slit coating was evaluated. The film thickness distribution of the coating film on the surface of the substrate to which the coating film (after drying) was attached was measured by a film thickness measuring device (Filmetrics Japan, Inc., F20 film thickness measuring system) at 81 locations with a length of 90 mm and a width of 90 mm, except for the 10 mm end of the coating part, at intervals of 10 mm, and the maximum and minimum differences were set as TTV (Total thickness variation). In each embodiment and comparative example, the average value of 3 samples was used.

TTV was measured in the area excluding 10mm from the end of the coating.

1μm：優良

1μm: Excellent

2μm：良 >1μm,

2μm: Good

>2μm: below standard

<Drying time after application>

In the above drying process, the time required for drying after being placed on a heating plate was evaluated. When a specified time has passed, the surface of the coated part is touched with a cotton swab. If a mark is left, it is considered to be incompletely dried. If no mark is left, it is considered to be completely dried. In each embodiment and comparative example, the average value of three samples is used. In addition, the drying time is measured at 100°C.

300sec：優良

300sec: Excellent

400：良 >300sec,

400: Good

>400sec: below standard

<Nozzle head contamination after cleaning>

In the above film-making process, the cleaning liquid of the composition shown in the table was poured into a bucket, and the nozzle head was immersed in the cleaning liquid at 23°C for the time shown in the table in such a way that the narrow slit of the nozzle head was immersed in the cleaning liquid, thereby evaluating the contamination of the nozzle head after the nozzle head was cleaned. In each embodiment and comparative example, it was adopted in 3 tests. In addition, the drying time set at 100°C was measured.

No contamination was confirmed in 3 times: None

Contamination confirmed more than once in 3 times: Yes

<Adhesion of coating film to components (Sia’s test)>

Sia's test was performed on the dried coating films formed by the above-mentioned slit coating on various substrates listed in Tables 1 to 9. The measuring device used was (Condor Sigma welding tester manufactured by XYZTEC). The test was performed as follows, that is, the dried film after the above-mentioned substrate coating was exposed to an exposure amount of 400mJ/ ^cm2 using a negative photomask capable of irradiating a 100μm square pattern, and the exposed film was developed with cyclopentanone after 30 minutes, and then rinsed with PGMEA to form a 100μm square film, and the film was pressed from the side at 10μm/s using (a needle arranged at a position 5μm from the base). In each embodiment and comparative example, the average value of three samples was adopted.

<10g: below standard

10g、<40g：良

10g, <40g: Good

40g：優良

40g: Excellent

The same Sia’s test was performed on a Cu electroplated substrate, an Al-Si-Cu alloy electroplated substrate, a Ti sputtered substrate, and a Ni sputtered substrate with a coating film attached. Furthermore, for Examples 32 to 36, the same Sia’s test was also performed on a Si substrate with a coating film attached. The evaluation criteria were also the same.

<Moisture resistance>

In addition, PCT (pressure pot test) was performed on Cu electroplated substrates and Ti sputtered substrates with coating films attached. The PCT test device used was (EHS-412 M manufactured by ESPEC CORP.). The coating film treatment conditions were set to 121°C, 100% relative humidity (RH), and 500 hours. The coating film after treatment was evaluated for adhesion (Sia’s test) under the same conditions as the above-mentioned <Coating film component adhesion> test. The evaluation criteria were also the same.

sec: seconds, min: minutes

*1 Soaking: Soaking when the nozzle is on standby: Soaking 30 seconds after application, spitting out 30 seconds after soaking

*2Comparison Example 2: ※If it is 100% DMSO, it will absorb moisture in the air and cannot be dried.

Poor dissolution: coating cannot be performed because the solid components cannot be dissolved in the solvent

Unable to measure: Unable to measure due to failure to apply paint

Not practicable: Adhesion testing could not be performed due to failure to apply the coating

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

Surfactant (MEGAFACE [trade name], DIC)

Water solubility is expressed in terms of the amount (g) dissolved in 100g of water at 23°C and expressed in mass %. Molecular weight is the weight average molecular weight.

(C) Photoradical polymerization initiator

C-1: Made by BASF, IRGACURE OXE-01

C-2: The following compound

(D) Free radical polymerizable compounds

D-1: Shin Nakamura Chemical Co., Ltd., NK ester A-9300

D-2: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer)

(E)Polymerization inhibitor

E-1: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-2: 4-methoxyphenol

(F) Migration inhibitor (rust inhibitor)

F-2: 1H-tetrazole

(G) Metal adhesion improver (silane coupling agent)

G-1: Made by Shin-Etsu Chemical Co., Ltd., Model: KBM-602

G-2: The following compound (where Et represents an ethyl group)

(H) Hardening accelerator (thermal alkali generator)

H-1: The following compound

H-2: The following compound

As plasticizers, O-180A, O-130P, and D-32 (all manufactured by ADEKA CORPORATION) are used in each table.

As can be seen from the above results, in the present invention, when implementing slit coating, if a film-forming composition containing a polyimide precursor, a specific solvent, and a surfactant or a plasticizer is used, even when a coating film is formed on a metal surface, a good surface shape of the coating film is obtained. In addition, in a preferred embodiment of the present invention, good performance is obtained in the coating property of the film-forming composition, the surface uniformity after coating and drying, the drying time after coating, the nozzle contamination after nozzle cleaning, and the component adhesion of the coating film.

<Exposure and development example>

The film-forming composition prepared in Example 1 was applied to a copper wafer (metal layer, equivalent to a member containing metal) by slit coating to form a coating film. The obtained coating film was dried on a heating plate at 100°C for 5 minutes to obtain a uniform preliminary cured film (film of the film-forming composition) with a thickness of about 15 μm. It was exposed using an exposure device (Karl-Suss MA150 [trade name]) through a mask having a line and space pattern (step: 5 to 20 μm). The exposure was performed using a high-pressure mercury lamp, and the exposure energy was calculated to be 500 mJ/cm ² at a wavelength of 365 nm.

The pre-cured film after exposure was dissolved in cyclopentanone for 75 seconds and immersion developed. The line width of the developed part was evaluated according to the following criteria. It was confirmed that the exposed width of the base substrate after development was within ±10% of the mask size and good exposure and development could be performed.

The formed resin pattern is heated at 250°C for 3 hours to cause the polyimide precursor to undergo a cyclization reaction to form a polyimide resin, thereby obtaining a resin pattern that is mechanically stable and strong despite being a fine pattern.

It can be seen that the produced resin pattern is composed of polyimide, so it has excellent insulation properties, and as mentioned above, it has good compatibility with metals and can better cope with fine processing, so it is particularly suitable for the manufacture of the redistribution layer of WL-CSP (wafer-level chip scale package).

In Example 1, the polyimide precursor A-1 was changed to polyimide precursor A-2 or A-3, and the same method was used. As in Example 1, an excellent effect was obtained. On the other hand, in Comparative Example 1, the polyimide precursor A-1 was changed to polyimide precursor A-2 or A-3, and the same method was used. As in Comparative Example 1, the surface shape after coating and drying was poor.

21‧‧‧Nozzle head

22‧‧‧Nozzle cleaner

23‧‧‧Transportation Department

21a‧‧‧Resin

24‧‧‧Roller

25‧‧‧Roller Groove

25b‧‧‧Liquid removal scraper

25a‧‧‧Cleaning fluid

30‧‧‧Substrate

100‧‧‧Narrow seam coating device

d3‧‧‧Direction

Claims (22)

A method for manufacturing a film, comprising a process of slit coating a component using a composition, the component at least partially comprising a metal, wherein the composition comprises: a polyimide precursor; at least two solvents having different solubility at 23°C relative to the polyimide precursor; and at least one selected from the group consisting of a surfactant and a plasticizer, the surfactant being a compound having a weight average molecular weight of 5,000 or less and having a solubility in water at 23°C of 0.1 mass % or more, the surfactant comprising at least one selected from the group consisting of MEGAFACE F-444, MEGAFACE F-430, MEGAFACE F-510 and MEGAFACE F-511, and the plasticizer being an epoxy plasticizer. The method for manufacturing the film as described in item 1 of the patent application scope includes a nozzle cleaning process of cleaning the nozzle head with a cleaning liquid after the slit coating process. The method for manufacturing a film as described in item 2 of the patent application scope, wherein the process for performing slit coating includes a nozzle standby process, in which the nozzle head is immersed in an immersion liquid, and the immersion liquid is a liquid having a composition of the same as that of the cleaning liquid by more than 90% by mass. A method for manufacturing a membrane as described in item 2 of the patent application, wherein the cleaning solution contains the solvent with the highest solubility in the polyimide precursor at 23°C among the at least two solvents. A method for manufacturing a membrane as described in item 2 of the patent application, wherein the cleaning solution contains the solvent with the lowest solubility in the polyimide precursor at 23°C among the at least two solvents. A method for manufacturing a membrane as described in item 3 of the patent application, wherein the immersion solution contains the solvent with the highest solubility of the polyimide precursor at 23°C among the at least two solvents. A method for manufacturing a membrane as described in item 3 of the patent application, wherein the immersion solution contains the solvent with the lowest solubility in the polyimide precursor at 23°C among the at least two solvents. The method for manufacturing a film as described in item 1 or 2 of the patent application scope has an exposure process for exposing the film formed by the slit coating and a development process for developing the exposed film. The method for manufacturing a film as described in item 1 or 2 of the patent application scope further includes a heating process for heating the film. A method for producing a film as described in item 1 or 2 of the patent application, wherein the composition contains a plasticizer. A method for manufacturing a laminate, which comprises performing the method for manufacturing a film as described in any one of items 1 to 10 of the patent application scope multiple times. The method for manufacturing a laminate as described in Item 11 of the patent application scope also includes a process for applying a metal layer to the film. A method for manufacturing a semiconductor device, wherein a film is configured with a chip manufactured by the film manufacturing method described in any one of items 1 to 10 of the patent application scope. A method for manufacturing a semiconductor device, wherein a multilayer body is configured with a chip manufactured by the method for manufacturing a multilayer body as described in item 11 or 12 of the patent application scope. A film-forming composition, which is a film-forming composition used in a manufacturing method as described in any one of items 1 to 10 of the scope of the patent application, the film-forming composition contains a polyimide precursor, at least two solvents having different solubility at 23°C relative to the polyimide precursor, and at least one selected from the group including a surfactant and a plasticizer, the surfactant is a compound with a weight average molecular weight of 5,000 or less, and a solubility in water at 23°C of 0.1 mass % or more, the surfactant includes at least one selected from the group consisting of MEGAFACE F-444, MEGAFACE F-430, MEGAFACE F-510 and MEGAFACE F-511, and the plasticizer is an epoxy plasticizer. The film-forming composition as described in item 15 of the patent application, wherein the polyimide precursor is a condensate of a dicarboxylic acid or a dicarboxylic acid derivative and a diamine. The film-forming composition as described in item 15 or 16 of the patent application scope, wherein among the at least two solvents, the solvent with the highest solubility of the polyimide precursor is a sulfone solvent, and among the at least two solvents, the solvent with the lowest solubility of the polyimide precursor is a ketone or lactone solvent. The film-forming composition as described in item 15 or 16 of the patent application, wherein the ratio of the total mass of the solvents in which the solubility of the polyimide precursor is higher than the following average value among the at least two solvents to the total mass of the solvents in which the solubility of the polyimide precursor is lower than the following average value among the at least two solvents is 10:90~45:55; the average value is the average value of the solubility of the solvent with the highest solubility at 23°C of the polyimide precursor and the solubility of the solvent with the lowest solubility at 23°C of the polyimide precursor. The film-forming composition as described in item 15 or 16 of the patent application, wherein the content of the surfactant in the solid component is 0.005-2 mass %. The film-forming composition as described in item 15 or 16 of the patent application, wherein the plasticizer is epoxidized oil. The film-forming composition as described in item 15 or 16 of the patent application, wherein the content of the plasticizer in the solid component is 0.005-2 mass %. A film-forming composition as described in item 15 or 16 of the patent application, wherein the film-forming composition contains a plasticizer.