KR102433579B1 - 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 - Google Patents

Abstract

A polyimide precursor, at least two solvents having different solubility at 23° C. with respect to the polyimide precursor, and a composition containing at least one selected from the group consisting of a surfactant and a plasticizer are used, and a slit is formed on the member. It relates to a method for producing a film, comprising a step of coating, wherein the member contains a metal at least in part thereof. Moreover, this invention relates to the manufacturing method of the laminated body which concerns on the manufacturing method of this film|membrane, the manufacturing method of a semiconductor device, and the composition for film formation.

Description

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

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

Since polyimide resin is excellent in heat resistance and insulation, it is applied for various uses. Although the use is not specifically limited, When the semiconductor device for mounting is given as an example, the material of an insulating film, a sealing material, or its use as a protective film is mentioned. Moreover, it is used also as a base film, a coverlay, etc. of a flexible board|substrate.

Generally, said polyimide resin has low solubility with respect to a solvent. Therefore, the method of melt|dissolving in a solvent in the polyimide precursor state before cyclization is used frequently. Thereby, excellent handling can be realized, and when manufacturing each product as described above, it can be applied and processed in various forms on a substrate or the like. The polyimide precursor can then be heated to form a cured article. In addition to the high performance of the polyimide resin, from the viewpoint of such excellent manufacturing adaptability, its industrial application development is increasingly expected.

On the other hand, in patent document 1, slit application|coating of the resin composition containing surfactant is described.

Patent Document 1: Japanese Patent Application Laid-Open No. 2013-243121

Here, as described in patent document 1, the technique of making the composition containing a polyimide precursor into a film|membrane by slit application|coating (slit coat) is known. However, it has been found that when the slit coat target of the polyimide precursor composition contains a metal on the surface, the surface of the film may become a so-called "orange peel".

An object of the present invention is to solve the above problems, and even when a coating film is formed on a metal surface, a slit coat capable of suppressing the occurrence of "orange peel" and achieving a good surface appearance is used. It aims at providing the composition for film formation suitable for use with respect to the manufacturing method of a film|membrane, the manufacturing method of a laminated body, the manufacturing method of a semiconductor device, and these manufacturing methods.

As a result of this inventor's examination under the said subject, when the composition containing a polyimide precursor was apply|coated in layer by the slit coat method, it discovered that a Bernard cell generate|occur|produced during drying and the surface became orange peel shape. And the composition (coating liquid for film formation) containing a polyimide precursor WHEREIN: As a solvent, at least 2 types of solvent from which the solubility in 23 degreeC with respect to a polyimide precursor differs is used, and also to the said composition, an interface It discovered that the said subject was solved by mix|blending at least 1 sort(s) chosen from the group which consists of an activator and a plasticizer.

Specifically, by the following means <1>, preferably by <2> to <23>, the said subject was solved.

<1> A polyimide precursor, at least two solvents having different solubility at 23° C. with respect to the polyimide precursor, and a composition containing at least one selected from the group consisting of surfactants and plasticizers; A method for producing a film, comprising the step of performing a slit coat on the film, wherein the member contains a metal at least in part thereof.

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

<3> The film production method according to <1> or <2>, including a head cleaning step of cleaning the nozzle head with a cleaning liquid after the step of performing slit coating.

<4> in the step of performing the slit coating, including a head waiting step, wherein in the head waiting step, the nozzle head is immersed in an immersion liquid, and the immersion liquid is in common with the cleaning liquid by 90% by mass or more The method for producing a film according to <3>, which is a liquid having a composition.

<5> The method for producing a film according to <3> or <4>, wherein the cleaning liquid contains a solvent having the highest solubility at 23° C. of the polyimide precursor among the at least two solvents.

<6> The method for producing a film according to any one of <3> to <5>, wherein the cleaning liquid contains a solvent having the lowest solubility at 23° C. of the polyimide precursor among the at least two solvents.

The <7> said immersion liquid contains the solvent with the highest solubility in 23 degreeC of the said polyimide precursor among the said at least 2 types of solvents, The manufacturing method of the film|membrane as described in <4>.

<8> The manufacturing method of the film|membrane as described in <4> or <7> in which the said immersion liquid contains the solvent with the lowest solubility in 23 degreeC of the said polyimide precursor among the said at least 2 types of solvents.

<9> The method for producing a film according to any one of <1> to <8>, comprising an exposure step of exposing the film formed by the slit coat, and a developing step of developing the exposed film.

<10> The method for producing a film according to any one of <1> to <9>, further comprising a heating step of heating the film.

<11> A method for producing a laminate, in which the method for producing a film according to any one of <1> to <10> is performed a plurality of times.

<12> The manufacturing method of the laminated body as described in <11> including the process of applying a metal layer to the said film|membrane.

<13> A method of manufacturing a semiconductor device in which a chip is disposed on a film manufactured by the method according to any one of <1> to <10>.

<14> A method for manufacturing a semiconductor device in which a chip is disposed on a laminate manufactured by the method according to <11> or <12>.

<15> It is the composition for film formation used by the manufacturing method in any one of <1>-<10>, Comprising: At least 2 types of solvent from which a polyimide precursor and the solubility in 23 degreeC with respect to the said polyimide precursor differ differ. And, a film-forming composition comprising at least one selected from the group consisting of surfactants and plasticizers.

<16> The film-forming composition according to <15>, wherein the polyimide precursor is a condensate of a dicarboxylic acid and a diamino compound.

<17> Among the at least two solvents, the solvent having the highest solubility of the polyimide precursor is a sulfoxide or lactam solvent, and among the at least two solvents, the solvent having the lowest solubility of the polyimide precursor The film-forming composition according to <15> or <16>, wherein the solvent is a ketone or a lactone.

<18> The total mass of solvents in which the solubility of the polyimide precursor is higher than the following average value among the at least two solvents, and the total amount of solvents in which the solubility of the polyimide precursor is lower than the following average value among the at least two solvents The composition for film formation according to any one of <15> to <17>, wherein the mass ratio is 10:90 to 45:55;

The said average value is the average value of the solubility of the solvent with the highest solubility in 23 degreeC of a polyimide precursor, and the solubility of the lowest solvent in 23 degreeC of a polyimide precursor.

<19> The film-forming composition according to any one of <15> to <18>, wherein the surfactant contains a fluorine atom.

<20> The composition for film formation according to <19>, wherein the surfactant is a compound having a weight average molecular weight of 5,000 or less containing a perfluoroalkyl group and is soluble in water.

<21> The film-forming composition according to any one of <15> to <20>, wherein the content of the surfactant is 0.005 to 2 mass% in solid content.

<22> The film-forming composition according to any one of <15> to <21>, wherein the plasticizer is an epoxidized oil.

<23> The film-forming composition according to any one of <15> to <22>, wherein the content of the plasticizer is 0.005 to 2 mass% in solid content.

ADVANTAGE OF THE INVENTION According to this invention, in a slit coat, even when a resin coating film is formed on the metal surface, generation|occurrence|production of an "orange peel" can be suppressed, and a favorable surface image can be achieved.

BRIEF DESCRIPTION OF THE DRAWINGS It is process explanatory drawing (1) for demonstrating the preferable embodiment of the slit coat applied in this invention by a schematic side view.
It is process explanatory drawing (2) for demonstrating preferable embodiment of the slit coat applied in this invention in a schematic side view.
It is process explanatory drawing (3) for demonstrating preferable embodiment of the slit coat applied in this invention in a schematic side view.

Although description of the components in this invention described below may be made based on typical embodiment of this invention, this invention is not limited to such an embodiment.

In the description of the group (atomic group) in the present specification, the description not describing substitution and unsubstituted includes those having no substituent and those having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams in exposure unless otherwise specified. Moreover, as light used for exposure, actinic rays or radiations, such as a bright-line spectrum of a mercury vapor lamp, and the deep ultraviolet, extreme ultraviolet (EUV light), X-rays, and an electron beam, generally typified by an excimer laser.

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

In this specification, "(meth)acrylate" represents both or any of "acrylate" and "methacrylate", and "(meth)acryl" is a term of "acryl" and "methacrylic". Both or either one is shown, and "(meth)acryloyl" shows both or either of "acryloyl" and "methacryloyl".

In the present specification, the term "process" is included in this term as long as the desired action of the process is achieved even if it is not clearly distinguishable from other processes as well as independent processes.

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to a gel permeation chromatography (GPC) measurement, unless it demonstrates in particular. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), and a guard column HZ-L, TSKgel Super HZM-M as a column. , TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) can be obtained by using any one or more. Unless otherwise specified, the eluent shall be measured using THF (tetrahydrofuran). In addition, unless otherwise indicated, detection shall use the wavelength 254nm detector of UV rays (ultraviolet rays).

The shape, dimension, number, arrangement location, etc. illustrated in the drawing are arbitrary and are not limited.

The method for producing a film of the present invention comprises a polyimide precursor, at least two solvents having different solubility in the polyimide precursor at 23°C, and at least one selected from the group consisting of a surfactant and a plasticizer. It is characterized by including the step of performing a slit coat on the member which contains a metal at least in part using. Thereby, in a slit coat, even when a coating film is formed on the metal surface, generation|occurrence|production of an "orange peel" can be suppressed and a favorable surface image (glossy) can be achieved.

After setting it as a coating film, a polyimide precursor is heated and hardened|cured. That is, at the stage of application|coating, the coating film was a fluid liquid phase, and as a result, it was estimated that orange peel was generate|occur|produced. And in order to suppress orange peel, it was estimated that it was important to consider the following points as a result.

(1) In order to suppress convection at an early stage during drying, a solvent having a low solubility is further employed in a solvent having a high solubility, or

(2) employing a surfactant to lower the surface tension of the coating film, or

(3) Add plasticizer to avoid continuation of internal convection by drying the surface first

And, by using 2 or more types of solvents from which solubility differs as mentioned above, and using at least 1 type selected from the group which consists of surfactant and a plasticizer, orange peel was suppressed and it succeeded in improvement of the surface appearance. Moreover, it succeeded also in the improvement of the adhesiveness of a polyimide resin layer and a metal (for example, a metal layer). In particular, by using a predetermined surfactant, it was also successful in obtaining excellent adhesion to copper (eg, a copper layer).

Hereinafter, the present invention will be described in detail.

<Slit coat>

BRIEF DESCRIPTION OF THE DRAWINGS It is process explanatory drawing (1) for demonstrating the preferable embodiment of the slit coat applied in this invention by a schematic side view. The coating apparatus 100 of this embodiment is equipped with the conveyance part 23 which conveys the board|substrate 30, and the support stage (not shown) which supports a board|substrate from below. A resist (resin) 21a is discharged to the substrate 30 from the nozzle head 21 through a slit-shaped nozzle, and the substrate 30 is conveyed in the direction d3 (slit coating step). The conveyance part 23 can be comprised by the some conveyance roller and the conveyance roller drive part which rotates these. The nozzle head 21 can be raised and lowered in the vertical direction by watching the timing at which the transfer unit transfers the substrate 30 . Similarly, the support stage (not shown) can also be moved and retracted from just below the nozzle head. At this time, it is possible to wait for the nozzle head and wait for the next substrate to be sent (head waiting process). You may perform the immersion process (immersion process process) and washing process (head washing process) of the nozzle head shown below in the head standby process between this slit coating process or after the slit coating process.

In the apparatus 100 of this embodiment, the nozzle head cleaner 22 is arrange|positioned just below a nozzle head. When the discharge of the resin to the substrate is finished, the nozzle head is lowered (d1) perpendicular to the application surface to immerse the nozzle head 21 in the immersion liquid provided in the nozzle head cleaner 22 (FIG. 2). The time for immersing the nozzle head in the immersion liquid in the cleaner is, for example, preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and still more preferably 0.5 minutes or more. As an upper limit, it is preferable that it is 10 minutes or less, It is more preferable that it is 8 minutes or less, It is more preferable that it is 5 minutes or less. Thereby, the tip of the nozzle head 21 can be cleaned.

3 : is an apparatus side view explaining the head maintenance process different from the said FIG. 1, FIG. 2, and shows the aspect of maintenance (cleaning) of a nozzle head. The apparatus of this embodiment is equipped with the roller 24 which rotates in the d2 direction. The roller bat 25 is filled with a cleaning liquid 25a to immerse the lower portion of the roller 24 . The apparatus 100 of this embodiment is further equipped with the liquid cutting blade 25b. The roller 24 and the roller bat 25 constitute the maintenance part 26 . The maintenance unit can be raised and lowered in a direction perpendicular to the substrate surface. By providing such a maintenance part, the apparatus of this embodiment does not lower|fall d5 the nozzle head 21 in a maintenance process WHEREIN: Also by raising the maintenance part 26 (d4) by making it d4, the nozzle head 21 ), it is possible to perform maintenance (cleaning). In the maintenance section, the liquid flowing from d5 is switched to the cleaning liquid. The time for flowing the cleaning liquid to the nozzle head is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and still more preferably 5 minutes or longer. As an upper limit, it is preferable that it is 120 minutes or less, It is more preferable that it is 60 minutes or less, It is more preferable that it is 30 minutes or less. Thereby, the nozzle head 21 can be washed.

In this invention, as mentioned above, in the process of performing slit coating, it is preferable to include a head waiting process. In the head standby step, it is preferable that the head is immersed in the immersion liquid. The immersion liquid is preferably a liquid having a composition common to the washing liquid and 90% by mass or more, more preferably a liquid having a composition in common to 95% by mass or more, and still more preferably the same composition.

The immersion liquid and the washing liquid are preferably a liquid having a composition common to 90% by mass or more with the solvent in the film-forming composition with respect to the type or mixing ratio of the compound, respectively, and a liquid having a composition in which 95% by mass or more is common It is more preferable, and it is more preferable that it is the same composition.

It is preferable that the washing|cleaning liquid also contains the solvent with the highest solubility in 23 degreeC of a polyimide precursor among at least 2 types of solvents contained in the composition for film formation. Moreover, it is preferable that a washing|cleaning liquid contains the solvent with the lowest solubility in 23 degreeC of a polyimide precursor among at least 2 types of solvents contained in the composition for film formation. In addition, among the at least two solvents contained in the film-forming composition, both a solvent having the highest solubility at 23 ° C. of the polyimide precursor and a solvent having the lowest solubility at 23 ° C. of the polyimide precursor are included. more preferably.

It is preferable that an immersion liquid also contains the solvent with the highest solubility in 23 degreeC of a polyimide precursor among at least 2 types of solvents contained in the composition for film formation. Moreover, it is preferable that an immersion liquid contains the solvent with the lowest solubility in 23 degreeC of a polyimide precursor among at least 2 types of solvents contained in the composition for film formation. In addition, among the at least two solvents contained in the film-forming composition, both a solvent having the highest solubility at 23 ° C. of the polyimide precursor and a solvent having the lowest solubility at 23 ° C. of the polyimide precursor are included. more preferably.

In addition, about a slit coat and the apparatus applicable to it, Unexamined-Japanese-Patent No. 2009-070973 can be considered into consideration, and the matter described there is integrated in this specification.

<Composition for film formation>

<<Polyimide Precursor>>

It is preferable that the repeating structural unit (structural unit) represented by following formula (1) is included as a polyimide precursor.

[Formula 1]

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

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

<<<R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a straight-chain or branched aliphatic group, a cyclic aliphatic group, and a group consisting of an aromatic group, a heteroaromatic group, or a combination thereof, and a linear aliphatic group having 2 to 20 carbon atoms and 3 to 20 carbon atoms. A group consisting of a branched aliphatic group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

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

Specifically, the diamine preferably contains a group consisting of a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And it is more preferable that it is a diamine containing a C6-C20 aromatic group. Examples of the aromatic group include the following.

[Formula 2]

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and these It is preferably a group selected from combinations, more preferably a group selected from a single bond or an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- and -SO ₂ - and 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 - do.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexene. three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus and isophoronediamines; Meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether , 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodi Phenylsulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexa Fluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone , bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-amino) Phenoxy)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'-di Methyl-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'-tetraaminobi Phenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'- diaminobife Nyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4 ,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- and 2,5-diaminocumene, 2,5-dimethyl- Paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl metaphenylenediamine, bis(3-aminopropyl)tetramethyl Disiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5- Diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis (4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexa Fluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, parabis(4-amino-2-tri Fluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy) ) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl Sulfone, 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′-hexafluorotolidine and 4 and at least one diamine selected from ,4'-diaminoquaterphenyl.

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

[Formula 3]

Moreover, the diamine which has at least two alkylene glycol units in a principal chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of either or both of an ethylene glycol chain and a propylene glycol chain in one molecule, More preferably, it is a diamine which does not contain an aromatic ring. Specific examples include 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) EDR-176, D-200, D-400, D-2000, D-4000 (trade names above, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) ) ethoxy) propoxy) propane-2-amine and 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, It is not limited to these.

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, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

[Formula 4]

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

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

It is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or (61) from the viewpoint of i-ray transmittance. In particular, it is more preferable that it is a divalent organic group represented by Formula (61) from a viewpoint of i line|wire transmittance and easy availability.

[Formula 5]

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 trifluoro is a methyl group.

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

[Formula 6]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

Examples of the diamine compound giving the structure of Formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-di aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. are mentioned. One of these may be used, or two or more types may be used in combination.

<<<R ¹¹⁵ >>>

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

[Formula 7]

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

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in Formula (1) include the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic acid dianhydride. As for tetracarboxylic dianhydride, only 1 type may be used and 2 or more types may be used for it. As for tetracarboxylic dianhydride, the compound represented by following formula (7) is preferable.

[Formula 8]

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

Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-di Phenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4 '-diphenylmethanetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3 ,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4 -dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride Water, 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) at least one selected from ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms paper is exemplified.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below are also mentioned as a preferable example.

[Formula 9]

<<<R ¹¹³ and R ¹¹⁴ >>>

R ¹¹³ and R ¹¹⁴ in Formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of ^R113 and ^R114 contains a radically polymerizable group, and it is more preferable that both contain a radically polymerizable group. As a radically polymerizable group, it is a group which can crosslinking-react by the action|action of a radical, and group which has an ethylenically unsaturated bond is mentioned as a preferable example.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryloyl group, and a group represented by the following formula (III).

[Formula 10]

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

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ — or a (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, it is a C1-C12 alkylene group) Preferably, 1-6 are more preferable, 1-3 are especially preferable; 1-12 are preferable, 1-6 are more preferable, and, as for the number of repetitions, 1-6 are especially preferable). In addition, a (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , dodecamethylene group, -CH ₂ CH(OH)CH ₂ -, and ethylene group, propylene group, trimethylene group, and -CH ₂ CH(OH)CH ₂ - are more preferable.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

Preferred embodiments of the polyimide precursor include an aliphatic group, an aromatic group and an arylalkyl group having 1, 2 or 3, preferably 1 acidic group as the monovalent organic group of ^R113 or ^R114 . . Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, the phenyl group which has an acidic radical, and the benzyl group which has an acidic radical are mentioned. As for an acidic radical, a hydroxyl group is preferable. 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 which improves the solubility of the developer is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in the organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As a monovalent organic group, it is preferable to contain a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and the alkyl group substituted by the aromatic group is more preferable.

As for carbon number of an alkyl group, 1-30 are preferable (in the case of a cyclic|annular form, 3 or more). The alkyl group may be linear, branched, or cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, and an iso group. and a propyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, bornyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. can be heard Among them, a cyclohexyl group is most preferred from the viewpoint of coexistence with high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.

Specific examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyri Dazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline a ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a cyanthrene ring, a chromene ring, a xanthene ring, a phenoxathiine ring, a phenothiazine ring, or a phenazine ring. The benzene ring is most preferred.

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structure. 10 mass % or more is preferable and, as for content of the fluorine atom in a polyimide precursor, 20 mass % or less is more preferable. Although there is no upper limit in particular, 50 mass % or less is practical.

Moreover, in order to improve adhesiveness with a board|substrate, you may copolymerize the aliphatic group which has a siloxane structure with the structural unit represented by Formula (1). Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(paraaminophenyl)octamethylpentasiloxane, and the like.

It is preferable that the structural unit represented by Formula (1) is a structural unit represented by Formula (1-A).

[Formula 11]

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

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in Formula (1), and have the same preferred ranges. do.

R ¹¹² has the same meaning as R ¹¹² in Formula (5), and the preferable range is also the same.

Polyimide precursor WHEREIN: Although 1 type may be sufficient as the repeating structural unit represented by Formula (1), 2 or more types may be sufficient as it. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included. Moreover, a polyimide precursor may also contain other types of structural units other than the structural unit of said Formula (1).

As one Embodiment of a polyimide precursor, 50 mol% or more of all structural units, Furthermore, 70 mol% or more, and especially 90 mol% or more are illustrated polyimide precursors which are structural units represented by Formula (1). As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of a polyimide precursor becomes like this. Preferably it is 2000-50000, More preferably, it is 5000-100000, More preferably, it is 10000-50000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-25000, More preferably, it is 2000-50000, More preferably, it is 4000-25000.

1.5-3.5 are preferable and, as for the dispersion degree of the molecular weight of a polyimide precursor, 2-3 are more preferable.

The polyimide precursor is a condensate of dicarboxylic acid or a dicarboxylic acid derivative and diamine. Preferably, dicarboxylic acid or a dicarboxylic acid derivative is obtained by halogenation using a halogenating agent, followed by reaction with diamine.

As a manufacturing method of a polyimide precursor, it is preferable to use the organic solvent in the case of reaction. The number of organic solvents may be one, and 2 or more types may be sufficient as them.

Although it can determine suitably according to a raw material as an organic solvent, Pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone are illustrated.

At the time of manufacture of a polyimide precursor, it is preferable that the process of depositing solid is included. Specifically, solid deposition can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving the polyimide precursor such as tetrahydrofuran in a soluble solvent.

The ratio of the polyimide precursor in the film-forming composition is preferably 60 mass % or more of the component (solid content) excluding the solvent, more preferably 70 mass % or more, still more preferably 75 mass % or more, It is preferable that it is 99 mass % or less, and it is more preferable that it is 95 mass % or less.

In the composition for film formation, only 1 type may be contained and 2 or more types of polyimide precursors may be contained. When two or more types are contained, it is preferable that a total amount becomes the said range.

<<Solvent>>

The composition (composition for film formation) used by the manufacturing method of a film|membrane contains as a solvent at least 2 types of solvent from which the solubility in 23 degreeC with respect to a polyimide precursor differs. It is specifically, preferable to use the mixed solvent of the solvent A which has higher solubility with respect to a polyimide precursor, and the solvent B with lower solubility in 23 degreeC at least as a solvent. Solubility is taken as quantity (g) of the polyimide precursor which melt|dissolves in 100 g of 23 degreeC solvent.

When there are three or more solvents, find the average value of the solubility of the highest solubility solvent and the lowest solvent, classify the solvent with a solubility higher than the average value as solvent A, and classify the solvent with a solubility lower than the average value as solvent B do. Moreover, when there are 3 or more types of solvents, it is preferable to make the solvent A of the highest solubility into solvent A, and it is preferable to use the thing of the lowest solubility as solvent B.

The difference in solubility between the solvent A and the solvent B is preferably 10 g or more, more preferably 15 g or more, and still more preferably 20 g or more. Although it does not specifically set as an upper limit, For example, it can be set as 50 g or less. By setting it as such a structure, the convection in the early stage during drying of a coating film can be suppressed more effectively.

It is preferable that it is 100 degreeC or more, and, as for the boiling point of the solvent A, it is more preferable that it is 110 degreeC or more, It is more preferable that it is 130 degreeC or more. It is preferable that it is 230 degrees C or less, and, as for an upper limit, it is more preferable that it is 210 degrees C or less, It is more preferable that it is 190 degrees C or less. By setting it as such a structure, there exists a tendency for the planar shape after application|coating to become more uniform.

It is preferable that the boiling point of the solvent B is 150 degreeC or more, It is more preferable that it is 180 degreeC or more, It is more preferable that it is 200 degreeC or more. It is preferable that it is 250 degrees C or less, and, as for an upper limit, it is more preferable that it is 230 degrees C or less, It is more preferable that it is 210 degrees C or less. By setting it as such a structure, there exists a tendency for the planar shape after application|coating to become more uniform.

It is preferable that the solvent A and the solvent B have a predetermined|prescribed difference in boiling point. It is preferable that it is 0 degreeC or more, and, as for the difference of a boiling point, it is more preferable that it is 10 degreeC or more, and it is more preferable that it is 20 degreeC or more. Moreover, it is preferable that it is 80 degrees C or less. By setting it as such a structure, it becomes possible to maintain a long time and planar shape more uniformly by the solvent B.

In addition, in this specification, a boiling point means the boiling temperature in 1013.25 hPa.

It is preferable that the solvent is an organic solvent.

Examples of the solvent classified as solvent A include sulfoxides, amides and lactams, and among them, sulfoxides are preferable.

Examples of the solvent classified into solvent B include esters, ethers, lactones, ketones, and aromatic hydrocarbons. Among them, lactones or ketones are preferable, and ketones are more preferable.

As the esters, for example, ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, lactones (γ-butyrolactone, ε-caprolactone, δ-valerolactone), alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (eg, 3-alkyloxypropionate methyl, 3-alkyloxy Ethyl propionate and the like (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg: 2-alkyloxypropionate methyl, 2-alkyloxypropionate ethyl, 2-alkyloxypropionate propyl, etc. (e.g., 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-e methyl oxypropionate, 2-ethoxypropionate ethyl)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2-methylpropionate ethyl (eg, 2-methoxy-2-methylpropionate methyl; 2-ethoxy-2-methyl ethyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. are mentioned as suitable. .

As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned as a suitable thing.

As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone etc. are mentioned as a suitable thing, for example.

As aromatic hydrocarbons, toluene, xylene, anisole, limonene etc. are mentioned as a suitable thing, for example.

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

Suitable amides include lactams (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone), N,N-dimethylacetamide, N,N-dimethylformamide, and the like. can

The content of the solvent is preferably such that the total solid concentration of the film-forming composition is 1 to 80% by mass, more preferably 1 to 60% by mass, and 5 to 40% by mass. It is more preferable to set it as quantity, and it is still more preferable to set it as 5-35 mass %.

To explain the preferable range for each solvent, the solvent A (if there are a plurality of types, based on their total mass) is preferably from 1 to 80% by mass, more preferably from 1 to 60% by mass in the film-forming composition. Preferably, it is more preferable that it is 5-40 mass %, and it is still more preferable that it is 5-30 mass %. Solvent B (based on the total mass when there is a plurality of types) is preferably 3-90 mass%, more preferably 6-80 mass%, and more preferably 10-60 mass%, in the film-forming composition. It is preferable, and it is still more preferable that it is 15-50 mass %.

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

<<Surfactant>>

It is preferable that the composition for film formation contains surfactant.

The surfactant is preferably a surfactant containing a fluorine atom, preferably a nonionic or anionic surfactant containing a fluorine atom, a nonionic or anionic oligomer containing a fluorine atom, or It is more preferable that it is a polymer surfactant. Moreover, it is preferable that a fluoroalkylene group is included, and, as for surfactant, it is more preferable that a perfluoroalkyl group is included.

The surfactant is preferably water-soluble. Soluble in this specification means that solubility is 0.05 mass % or more at 23 degreeC. Moreover, it is preferable that 0.1 mass % or more of surfactant dissolves in water at 23 degreeC, It is more preferable that it melt|dissolves 0.5 mass % or more, It is more preferable that it melt|dissolves 1 mass % or more. As an upper limit, it is practical that it is 5 mass % or less.

Surfactant may contain at least 1 sort(s) of a hydrophilic group, a lipophilic group, and an ultraviolet-reactive group in a molecule|numerator.

Especially, in this invention, it is preferable that it is a perfluoroalkyl group containing carboxylate (anionic type) from a viewpoint of moisture resistance becoming high. It is preferable that surfactant is soluble or slightly soluble in water (for example, 0.1 mass % or more), but insoluble in hydrocarbon solvent (for example, hexane or toluene). It is preferable that it is 10 mN/m or more, and, as for the surface tension of the 0.1 mass % solution with respect to water, it is more preferable that it is 15 mN/m or more. It is practical that the upper limit is 50 mN/m or less. The surface tension of the 0.1% solution with respect to PGME (propylene glycol monomethyl ether) is preferably more than 25 mN/m, more preferably 26 mN/m or more. It is practical that the upper limit is 70 mN/m or less.

Specific examples of the fluorine-based surfactants include: fluorine nut F-C430 and fluorine nut F-C431 (above, manufactured by Sumitomo 3M Co., Ltd.); Mega Park F-142D, Mega Park F-171, Mega Park F-172, Mega Park F-173, Mega Park F-177, Mega Park F-183, Mega Park F-410, Mega Park F-444, Mega Park F-470, Mega Park F-471, Mega Park F-478, Mega Park F-479, Mega Park F-480, Mega Park F-482, Mega Park F-483, Mega Park F-484, Mega Park F- 486, Mega Park F-487, Mega Park F-489, Mega Park F-553, Mega Park F-554, Mega Park F-556, Mega Park F-557, Mega Park F-569, Mega Park F-575, Megapac F-780F, Megapac F-781F, Megapac R30 (above, manufactured by DIC Corporation); Ftop EF301, Ftop EF303, Ftop EF351, Ftop EF352 (above, Shin-Akita Chemical Co., Ltd. make); SURFRON S381, SURFRON S382, SURFRON SC101, SURFRON SC105 (above, manufactured by Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Fine Chemicals, Inc.); BM-1000, BM-1100 (made by BMChemie), etc. are mentioned.

Speaking of surfactants of the Megapac series made by DIC, it is preferable that the hydrophilicity is high, and the content of fluorine atoms is more preferable. If the hydrophilic sequence is expressed as a part, F-410>F-444>F-430, F-510, F-511, F-569, F-553, F-477, F-556>>F-554. becomes a sequence. Regarding the fluorine atom content, the sequence is F-430>F-410, F-510, F-511>F-444>>F-569, F-553, F-554, F-477, F-556. . In terms of hydrophilicity and fluorine atom content, it is preferable that at least one is on the left (greater than) of >>, and in both, it is preferable that it is on the left (greater than) of >>.

Among surfactants, Megapac F-410 and F-444 (both brand names) showed favorable results in the adhesion test after PCT performed in the following examples. On the other hand, the F-510 was lagging behind. Also from this viewpoint, Megapac F-410 and F-444 are particularly preferable, and F-444 is particularly more preferable.

It is preferable that it is 30,000 or less, and, as for the weight average molecular weight of surfactant, it is more preferable that it is 10,000 or less, It is more preferable that it is 5,000 or less, It is still more preferable that it is 4,000 or less. As a lower limit, it is practical that it is 500 or more.

The molecular weight of the surfactant was determined by the method described in Example 1 of Examples of Japanese Patent Application Laid-Open No. 2001-208736, specifically, using Asahi Clean AK-225 SEC Grade 1 as a mobile phase, as a column for SEC, Using two PL gels 5 μm MIXED-E (inner diameter 7.5 mm, length 30 cm) connected in series from Polymer Laboratories, the mobile phase flow rate was 1.0 ml per minute and the column temperature was 37 ° C. Differential refractive index as a detector (RI) It is measured by the method with the polarity as - using a detector.

It is preferable that content of surfactant is 0.0008 mass % or more in solid content of the composition for film formation, It is more preferable that it is 0.005 mass % or more, It is more preferable that it is 0.01 mass % or more. As an upper limit, it is preferable that it is 5 mass % or less, It is more preferable that it is 4 mass % or less, It is still more preferable that it is 2 mass % or less, 1 mass % or less may be sufficient, 0.5 mass % or less, 0.1 mass % or less, 0.01 mass % or less may be

About the whole composition, it is preferable that it is 0.0001 mass % or more, It is more preferable that it is 0.0005 mass % or more, It is more preferable that it is 0.001 mass % or more. As an upper limit, it is preferable that it is 5 mass % or less, It is more preferable that it is 2 mass % or less, It is more preferable that it is 1 mass % or less.

It is preferable that content of surfactant with respect to 100 mass parts of polyimide precursors is 0.001 mass part or more, It is more preferable that it is 0.005 mass part or more, It is more preferable that it is 0.01 mass part or more. As an upper limit, it is preferable that it is 15 mass parts or less, It is more preferable that it is 10 mass parts or less, It is still more preferable that it is 5 mass parts or less, It is still more preferable that it is 2 mass parts or less, It is especially preferable that it is 1 mass part or less, 0.5 mass It is especially more preferable that it is less than a part, and it is most preferable that it is 0.1 mass part or less.

Only 1 type may be included and 2 or more types of surfactant may be included. When 2 or more types are included, it is preferable that a total amount becomes the said range.

By adjusting the surfactant within the above range, the surface tension of the coating film of the composition for film formation is lowered, the formation of a Bernard cell or its influence can be effectively suppressed, and the flatness of the film can be improved.

<<Plasticizer>>

The plasticizer used for the composition for film formation which concerns on embodiment of this invention is not specifically defined, such as the kind, A well-known plasticizer can be used.

Specifically, phthalic acid esters, adipic acid esters, trimellitic acid esters, polyesters, phosphoric acid esters, citric acid esters, epoxy-based plasticizers, sebacic acid esters, azelaic acid esters, maleic acid esters, and benzoic acid esters are exemplified, and epoxy-based esters are exemplified. A plasticizer is preferred.

Examples of the epoxy-based plasticizer include epoxidized oils (epoxidized soybean oil, epoxidized linseed oil) and epoxidized fatty acid alkyl (eg, octyl) esters.

As an epoxy plasticizer, it is preferable to have the epoxy group of following formula e1 or e2 in a molecule|numerator.

[Formula 12]

That is, those in which the formula e1 is introduced at the end or in the middle of the olefin chain or paraffin chain constituting the plasticizer, those in which the formula e2 is introduced in the middle of the chain, or both at the end and in the middle are introduced. It is preferable that the epoxy plasticizer is a fatty acid or a fat and oil, and it is more preferable that the carboxyl group is introduce|transduced into the said olefin chain or paraffin chain. However, a part or all of this carboxyl group may be esterified with an alkyl group etc. It is preferable that carbon number is 3-48, as for a plasticizer, 4-36 are more preferable, and 6-24 are still more preferable.

Specifically, ADEKA Co., Ltd., O-180A, O-130P, D-32, and D-55 (all are brand names) are mentioned, Among them, O-180A, O-130P, and D-32 are preferable.

It is preferable that the viscosity in 25 degreeC of a plasticizer is 40 mPa*s or more, It is more preferable that it is 100 mPa*s or more, It is more preferable that it is 200 mPa*s or more. As an upper limit, it is practical that it is 800 mPa*s or less. It is preferable that it is 8 or more, and, as for SP value, it is more preferable that it is 8.5 or more. Although there is no particular upper limit, 9.5 or less is practical.

It is preferable that content of a plasticizer is 0.0008 mass % or more in solid content of the composition for film formation, It is more preferable that it is 0.005 mass % or more, It is more preferable that it is 0.01 mass % or more. As an upper limit, it is preferable that it is 5 mass % or less, It is more preferable that it is 4 mass % or less, It is still more preferable that it is 2 mass % or less, 1 mass % or less may be sufficient, 0.5 mass % or less, 0.1 mass % or less, 0.01 mass % or less may be

It is preferable that content of the plasticizer with respect to 100 mass parts of polyimide precursors is 0.001 mass part or more, It is more preferable that it is 0.005 mass part or more, It is more preferable that it is 0.01 mass part or more. As an upper limit, it is preferable that it is 15 mass parts or less, It is more preferable that it is 10 mass parts or less, It is still more preferable that it is 5 mass parts or less, It is still more preferable that it is 2 mass parts or less, It is especially preferable that it is 1 mass part or less, 0.5 mass It is especially more preferable that it is less than a part, and it is most preferable that it is 0.1 mass part or less.

Only 1 type may be sufficient as a plasticizer, and 2 or more types may be included. When 2 or more types are included, it is preferable that a total amount becomes the said range.

By setting the plasticizer in the above range, it is preferable to prevent drying of the film surface, to avoid the continuous Bernard cell, and to obtain a better surface appearance of the coating film.

<<Photoinitiator>>

The composition for film formation may contain a photoinitiator. It is preferable that a photoinitiator is a photoradical polymerization initiator.

There is no restriction|limiting in particular as a photo-radical polymerization initiator which can be used by this invention, It can select suitably from well-known photo-radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the visible region from the ultraviolet region is preferable. Moreover, the activator which generate|occur|produces an active radical by generating a certain action with the photo-excited sensitizer may be sufficient.

It is preferable that the photoradical polymerization initiator contains at least 1 sort(s) of the compound which has a molar extinction coefficient of at least about 50 within the range of about 300-800 nm (preferably 330-500 nm). The molar extinction coefficient of a compound can be measured using a well-known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g/L using an ethyl acetate solvent.

As a photoradical polymerization initiator, a well-known compound can be used arbitrarily. For example, acylphosphine compounds such as halogenated hydrocarbon derivatives (eg, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, a compound having a trihalomethyl group, etc.) and acylphosphine oxide , hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds , a metallocene compound, an organoboron compound, an iron arene complex, and the like. For these details, Paragraph 0165 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0182 can be considered into consideration, and this content is integrated in this specification.

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

As a photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-oxide-based initiator described in JP-A 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 IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which the maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

As a metallocene compound, IRGACURE-784 (made by BASF) etc. are illustrated.

As a photoradical polymerization initiator, More preferably, an oxime compound is mentioned. By using an oxime compound, it becomes possible to improve an exposure latitude more effectively. An oxime compound has a wide exposure latitude (exposure margin), and since it also acts as a photocuring accelerator, it is especially preferable.

As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

As a preferable oxime compound, Paragraph 0080 of Unexamined-Japanese-Patent No. 2015-189883 - description of 0083 can be considered into consideration, and these content is integrated in this specification.

A photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, (alpha)-hydroxyketone compound, (alpha)-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metal from a viewpoint of exposure sensitivity. Rosene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxa A compound selected from the group consisting of a diazole compound and a 3-aryl substituted coumarin compound is preferred.

Moreover, the compound of Paragraph 0048 - 0055 of International Publication No. 2015/125469 can also be used as a photoradical polymerization initiator.

When a photoinitiator is included, it is preferable that the content is 0.1-30 mass % with respect to the total solid of the composition for film formation, More preferably, it is 0.1-20 mass %, More preferably, it is 0.5-15 mass %. and more preferably 1.0-10 mass %. The photoinitiator may contain only 1 type, and may contain it 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that the sum total is the said range.

<<thermal radical polymerization initiator>>

The composition for film formation may contain the thermal radical polymerization initiator.

A thermal radical polymerization initiator is a compound which generate|occur|produces a radical with the energy of heat, and initiates or accelerates|stimulates the polymerization reaction of the compound which has polymerizability. By adding a thermal radical polymerization initiator, since the polymerization reaction of a polyimide precursor can also be advanced with cyclization of a polyimide precursor, higher degree of heat resistance can be achieved.

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

When a thermal radical polymerization initiator is included, it is preferable that the content is 0.1-30 mass % with respect to the total solid of the composition for film formation, More preferably, it is 0.1-20 mass %, More preferably, it is 5-15 mass %. mass %. The thermal radical polymerization initiator may contain only 1 type, and may contain it 2 or more types. When 2 or more types of thermal radical polymerization initiators are contained, it is preferable that the sum total is the said range.

<<Polymerizable compound>>

<<<Radically Polymerizable Compound >>>

It is preferable that the composition for film formation contains a radically polymerizable compound.

The radically polymerizable compound can use the compound which has a radically polymerizable group. As a radically polymerizable group, group which has ethylenically unsaturated bonds, such as a vinylphenyl group, a vinyl group, a (meth)acryloyl group, and an allyl group, is mentioned. A radically polymerizable group has a preferable (meth)acryloyl group.

One or two or more may be sufficient as the number of radically polymerizable groups which a radically polymerizable compound has, However, It is preferable to have two or more radically polymerizable groups, and, as for a radically polymerizable compound, it is more preferable to have three or more. 15 or less are preferable, as for an upper limit, 10 or less are more preferable, and 8 or less are still more preferable.

2000 or less are preferable, as for the molecular weight of a radically polymerizable compound, 1500 or less are more preferable, and 900 or less are still more preferable. As for the minimum of the molecular weight of a radically polymerizable compound, 100 or more are preferable.

From the viewpoint of developability, the composition for film formation preferably contains at least one difunctional or higher radically polymerizable compound containing two or more polymerizable groups, and contains at least one trifunctional or higher radical polymerizable compound more preferably. Moreover, the mixture of a bifunctional radically polymerizable compound and trifunctional or more than trifunctional radically polymerizable compound may be sufficient. In addition, the number of functional groups of a radically polymerizable compound means the number of radically polymerizable groups in 1 molecule.

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

Moreover, as for a radically polymerizable compound, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol. Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propane tri (acryloyloxy) A compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol such as propyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and then (meth) acrylated compound, Japanese publication Urethane (meth)acrylates described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 48-064183 , polyester acrylates described in Japanese Patent Publication No. 49-043191 and Japanese Patent Publication No. 52-030490, and epoxy acrylates that are reaction products of an epoxy resin and (meth)acrylic acid. acrylates, methacrylates, and mixtures thereof. Moreover, the compound of Paragraph 0254 of Unexamined-Japanese-Patent No. 2008-292970 - 0257 is also suitable. Moreover, polyfunctional (meth)acrylate obtained by making polyfunctional carboxylic acid react with cyclic ether groups, such as glycidyl (meth)acrylate, and the compound which has an ethylenically unsaturated bond, etc. are mentioned.

Moreover, it has a fluorene ring and is ethylenic as described in Unexamined-Japanese-Patent No. 2010-160418, Unexamined-Japanese-Patent No. 2010-129825, Unexamined-Japanese-Patent No. 4364216 etc. as a preferable radically polymerizable compound other than what was mentioned above. It is also possible to use a compound having two or more groups having an unsaturated bond, or a cardo resin.

In addition, as other examples, specific unsaturated compounds described in Japanese Patent Application Laid-Open No. 46-043946, Japanese Unexamined Patent Publication No. Hei 01-040337, and Japanese Unexamined Patent Publication No. Hei 01-040336, and Japanese Unexamined Patent Publication No. Hei 02-025493 and the vinylphosphonic acid-based compounds described in the preceding paragraph. Moreover, the compound containing the perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Also, the Japan Adhesive Association Magazine vol. 20, No. 7, 300-308 (1984), those introduced as photopolymerizable monomers and oligomers can also be used.

In addition to the above, the compounds described in Paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 can also be preferably used, the contents of which are incorporated herein by reference.

Moreover, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described with the specific example as Formula (1) and Formula (2) in Unexamined-Japanese-Patent No. 10-062986 (meth)acrylated, A compound can also be used as a radically polymerizable compound.

Moreover, Paragraph 0104 of Unexamined-Japanese-Patent No. 2015-187211 - the compound of 0131 can also be used as another radically polymerizable compound, These content is integrated in this specification.

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

As a commercial item of a radically polymerizable compound, SR-494 which is a tetrafunctional acrylate which has four ethyleneoxy chains made by Sartomer, for example, SR- which is a bifunctional methacrylate which has four ethyleneoxy chains manufactured by Sartomer Co., Ltd. 209, 231, 239, manufactured by Nippon Kayaku Co., Ltd., DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, oil Retain oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Corporation), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical), Blemmer PME400 (Ni) Healing Co., Ltd.) and the like.

As a radically polymerizable compound, the oil described in Unexamined-Japanese-Patent No. 48-041708, Unexamined-Japanese-Patent No. 51-037193, Unexamined-Japanese-Patent No. Hei 02-032293, and Unexamined-Japanese-Patent No. Hei 02-016765. Retain acrylates, Japanese Patent Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, Japanese Patent Publication No. 62-039418 Ethylene oxide system described in Also suitable are urethane compounds having a skeleton. Moreover, as a radically polymerizable compound, it has an amino structure or a sulfide structure in a molecule|numerator, which is described in Unexamined-Japanese-Patent No. 63-277653, Unexamined-Japanese-Patent No. 63-260909, and Unexamined-Japanese-Patent No. Hei 01-105238. A compound may also be used.

A radically polymerizable compound which has acidic radicals, such as a carboxyl group and a phosphoric acid group, may be sufficient as a radically polymerizable compound. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is radically polymerizable by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group A compound is more preferable. Particularly preferably, in the radically polymerizable compound in which an acid group is given by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. is a phosphorus compound. As a commercial item, M-510, M-520 etc. are mentioned, for example as a polybasic acid modified|denatured acrylic oligomer made from Toagosei Corporation.

The preferable acid value of the radically polymerizable compound which has an acidic radical is 0.1-40 mgKOH/g, Especially preferably, it is 5-30 mgKOH/g. When the acid value of a radically polymerizable compound is the said range, it is excellent in manufacture and handleability, and by extension, it is excellent in developability. Moreover, polymerizability is favorable.

As the radically polymerizable compound, a monofunctional radically polymerizable compound can be preferably used. Examples of the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol ( Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol (meth)acrylic acid derivatives such as lycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; Allyl compounds, such as cydyl ether, diallyl phthalate, and triaryl trimellitate, etc. are used preferably. As a monofunctional radically polymerizable compound, since volatilization before exposure is suppressed, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable.

<<<Polymerizable compounds other than the above-mentioned radically polymerizable compounds >>>

The film-forming composition may further contain a polymerizable compound other than the radical polymerizable compound described above. Examples of the polymerizable compound other than the radical polymerizable compound described above include a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

(A compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)

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

[Formula 13]

(Wherein, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t valency of 1 to 200 carbon atoms, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ silver 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)

[Formula 14]

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

[Formula 15]

(wherein u represents an integer of 3 to 8, R ⁵⁰⁴ represents an organic group having a valence of 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ represents, 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)

As a specific example of the compound represented by Formula (AM4), 46DMOC, 46DMOEP (above, a brand name, Asahi Yukizai Kogyo Co., Ltd. product), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML -PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 ( brand name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like.

Moreover, as a specific example of the compound represented by Formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP , HMOM-TPPHBA, HMOM-TPHAP (above, brand name, manufactured by Honshu Chemical Industries, Ltd.), TM-BIP-A (brand name, manufactured by Asahi Yukizai Kogyo Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MW-100LM (above, a brand name, manufactured by Sanwa Chemical Co., Ltd.) is mentioned.

(Epoxy compound (compound having an epoxy group))

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in 1 molecule. Since the epoxy group undergoes a crosslinking reaction at 200° C. or less and a dehydration reaction resulting from crosslinking does not occur, film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective in low-temperature hardening of a composition, and suppression of the curvature of a film|membrane.

It is preferable that an epoxy compound contains a polyethylene oxide group. Thereby, an elastic modulus falls more and curvature can be suppressed. The polyethylene oxide group means that the number of structural units of ethylene oxide is two or more, and it is preferable that the number of structural units is 2-15.

As an example of an epoxy compound, Bisphenol A epoxy resin; bisphenol F-type epoxy resin; alkylene glycol-type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol-type epoxy resins such as polypropylene glycol diglycidyl ether; Although epoxy group containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, It is not limited to these. Specifically, Epiclone (registered trademark) 850-S, Epiclone (registered trademark) HP-4032, Epiclone (registered trademark) HP-7200, Epiclone (registered trademark) HP-820, Epiclone (registered trademark) HP-4700, Epiclone (registered trademark) EXA-4710, Epiclone (registered trademark) HP-4770, Epiclone (registered trademark) EXA-859 CRP, Epiclone (registered trademark) EXA-1514, Epiclone (registered trademark) ) EXA-4880, Epiclone (registered trademark) EXA-4850-150, Epiclone (registered trademark) EXA-4850-1000, Epiclone (registered trademark) EXA-4816, Epiclone (registered trademark) EXA-4822 (or higher) Brand name, Dainippon Ink Chemicals Co., Ltd.), Rika Resin (registered trademark) BEO-60E (brand name, Shin-Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (above brand name, manufactured by ADEKA Corporation) ) and the like. Among these, the epoxy resin containing a polyethylene oxide group is preferable at the point excellent in suppression of curvature and heat resistance. For example, Epiclone (registered trademark) EXA-4880, Epiclone (registered trademark) EXA-4822, and Likaresin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

(Oxetane compound (compound having an oxetanyl group))

Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, and 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. are mentioned. . As a specific example, Toagosei Co., Ltd. Aaron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be used suitably, These may be used individually or in mixture of 2 or more types do.

(benzoxazine compound (compound having a benzoxazolyl group))

A benzoxazine compound is preferable at the point that degassing does not generate|occur|produce at the time of hardening because of the crosslinking reaction derived from a ring-opening addition reaction, and also makes thermal contraction small and generation|occurrence|production of curvature is suppressed.

Preferred examples of the benzoxazine compound include B-a-type benzoxazine, B-m-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolak-type dihydrobenz oxazine compounds. These may be used independently or may mix 2 or more types.

When it contains a polymeric compound, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solid of the composition for film formation. As for a minimum, 5 mass % or more is more preferable. It is more preferable that it is 50 mass % or less, and, as for an upper limit, it is more preferable that it is 30 mass % or less.

Although a polymeric compound may be used individually by 1 type, it may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount becomes said range.

<<Migration inhibitor>>

It is preferable that the composition for film formation further contains a migration inhibitor. By including a migration inhibitor, it becomes possible to suppress effectively that the metal ion derived from a metal layer (metal wiring) moves into the film|membrane of the composition for film formation.

Although there is no restriction|limiting in particular as a migration inhibitor, A heterocyclic ring (pyrrole ring, furan ring, thiophen ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring compound having a ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compounds having , hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Moreover, an ion trapping agent which traps anions, such as a halogen ion, can also be used.

As other migration inhibitors, the antirust agent of Paragraph 0094 of Unexamined-Japanese-Patent No. 2013-015701, Paragraph 0073 of Unexamined-Japanese-Patent No. 2009-283711-0076, The compound of Paragraph 0052 of Unexamined-Japanese-Patent No. 2011-059656, The compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A can be used.

As a specific example of a migration inhibitor, the following compound is mentioned.

[Formula 16]

When the composition for film formation has a migration inhibitor, it is preferable that content of a migration inhibitor is 0.01-5.0 mass % with respect to the total solid of the composition for film formation, It is more preferable that it is 0.05-2.0 mass %, It is more preferable, 0.1- It is more preferable that it is 1.0 mass %.

The number of migration inhibitors may be one, and 2 or more types may be sufficient as them. When there are 2 or more types of migration inhibitors, it is preferable that the sum total is the said range.

<<Polymerization inhibitor >>

It is preferable that the composition for film formation contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p -benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol Terdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1- Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3 ,5-tert-butyl)phenylmethane etc. are used suitably. Moreover, the polymerization inhibitor of Paragraph 0060 of Unexamined-Japanese-Patent No. 2015-127817, and the compound of Paragraph 0031 - 0046 of International Publication No. 2015/125469 can also be used.

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

[Formula 17]

When the composition for film formation has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, based on the total solid content of the composition for film formation, It is more preferable that it is 0.05-2.5 mass %.

The number of polymerization inhibitors may be one, and 2 or more types may be sufficient as them. When the polymerization inhibitor is 2 or more types, it is preferable that the sum total is the said range.

<Metal adhesion improving agent>

It is preferable that the composition for film formation contains the metal adhesiveness improving agent for improving adhesiveness with the metal material used for an electrode, wiring, etc. As a metal adhesive improving agent, a silane coupling agent etc. are mentioned.

As an example of a silane coupling agent, Paragraph 0062 of Unexamined-Japanese-Patent No. 2014-191002 Paragraph 0062 - 0073, The compound of Paragraph 0063 - 0071 of International Publication No. 2011/080992 Paragraph 0060 - of Unexamined-Japanese-Patent No. 2014-191252 The compound of 0061, Paragraph 0045 of Unexamined-Japanese-Patent No. 2014-041264 - Paragraph 0052, The compound of Paragraph 0055 of International Publication No. 2014/097594 are mentioned. Moreover, as described in Paragraph 0050 - 0058 of Unexamined-Japanese-Patent No. 2011-128358, it is also preferable to use 2 or more types of different silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Et represents an ethyl group.

[Formula 18]

Moreover, the compound of Paragraph 0046 - 0049 of Unexamined-Japanese-Patent No. 2014-186186, Paragraph 0032 - 0043 of Unexamined-Japanese-Patent No. 2013-072935 can also be used as a metal adhesiveness improving agent.

To [ content of metal adhesive improving agent / 100 mass parts of polyimide precursors ], Preferably it is 0.1-30 mass parts, More preferably, it is the range of 0.5-15 mass parts, More preferably, it is the range of 0.5-5 mass parts. By setting it as more than the said lower limit, the adhesiveness of the film|membrane and a metal layer after a hardening process becomes favorable, and by setting it below the said upper limit, the heat resistance and mechanical properties of the film|membrane after a hardening process become favorable. The number of metal adhesive improving agents may be one, and 2 or more types may be sufficient as them. When using 2 or more types, it is preferable that the sum total is the said range.

<curing accelerator>

The composition for film formation may contain the hardening accelerator. A thermosetting accelerator may be sufficient as a hardening accelerator, and a photocuring accelerator may be sufficient as it.

<<thermal curing accelerator>>

It is preferable that a thermosetting accelerator generate|occur|produces a base by heating. A preferable range of the heating temperature (base generation temperature) is the same as the temperature specified in the heating step below. A salt of a tertiary amine or a quaternary ammonium cation with a carboxylate anion is preferred. It is preferable that this tertiary amine and a quaternary ammonium cation are represented by either of following formula (Y1-1) - formula (Y1-4).

[Formula 19]

R ^Y1 represents an organic group of n ^{Y valence (n Y is} an integer of 1 to 12), and is preferably a hydrocarbon group. As a hydrocarbon group, the group containing an alkane (C1-C12 is preferable, 1-6 are more preferable, and 1-3 are still more preferable), a group containing an alkene (C2-C12 is preferable, and , 2-6 are more preferable, 2-3 are more preferable), a group containing an aromatic hydrocarbon (C6-C22 is preferable, 6-18 are more preferable, 6-10 are still more preferable) , or a combination thereof. Among them, R ^Y1 is preferably an aromatic hydrocarbon group. R ^Y1 is a substituent T (hydroxyl group, carboxyl group, amino group (NR ^N ₂ ), alkoxyl group (C 1-12 is preferable, 1-6 are more preferable, in the range which does not impair the effect of this invention), 1-3 are more preferable), an acyl group (C2-C12 is preferable, 2-6 are more preferable, and 2-3 are more preferable), an alkoxycarbonyl group (C2-C12 is preferable, 2 -6 are more preferable, 2-3 are more preferable), an acyloxy group (C2-C12 are preferable, 2-6 are more preferable, and 2-3 are more preferable), a carbamoyl group (the number of carbon atoms) 1 to 12 are preferable, 1 to 6 are more preferable, and 1 to 3 are still more preferable) and R ^N is a hydrogen atom or a group having the same meaning as the group represented by R ^Y2 ).

R ^Y2 to R ^Y5 each independently represent a hydrogen atom or a hydrocarbon group (preferably C1-36, more preferably 1-24, and still more preferably 1-12), and an alkyl group (C1-C6 36 is preferable, 1-24 are more preferable, 1-23 are more preferable), an alkenyl group (C2-36 are preferable, 2-24 are more preferable, and 2-23 are still more preferable), alkynyl group (C1-C36 is preferable, 1-24 are more preferable, and 1-23 are more preferable), aryl group (C6-C22 is preferable, 6-18 are more preferable, 6- 10 is more preferable).

R ^Y6 is an alkyl group (C1-36 are preferable, 2-24 are more preferable, and 4-18 are still more preferable), an alkenyl group (C2-36 are preferable, 2-24 are more preferable, 4 ~18 is more preferable), an alkynyl group (C2-36 are preferable, 2-24 are more preferable, and 4-18 are still more preferable), an aryl group (C6-22 are preferable, 6- 18 is more preferable, and 6-10 are more preferable).

n ^Y represents the integer of 1-12, the integer of 1-6 is preferable, and the integer of 1-3 is more preferable.

n ^X represents the integer of 1-12, the integer of 1-6 is preferable, and the integer of 1-3 is more preferable.

In R ^Y2 to R ^Y6 , an alkyl group, an alkenyl group, and an alkynyl group may be cyclic or may be chained, and in the case of a chain, linear or branched may be sufficient. In an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, in the middle of the group or in connection with a parent nucleus, a linking group L (carbonyl group, oxygen atom, sulfur atom, NR ^N , alkylene group (C 1-12 is preferable, 1-6 are more preferable, and 1-3 are more preferable), an alkenylene group (C2-C12 is preferable, 2-6 are more preferable, and 2-3 are more preferable), an arylene group (the number of carbon atoms) 6 to 22 are preferable, 6 to 18 are more preferable, and 6 to 10 are still more preferable) or the linking group related to a combination thereof) may be interposed.

Each of R ^Y2 to R ^Y6 may combine two or more of them to form a ring.

R ^Y2 to R ^Y6 may have a substituent T.

R ^Y7 to R ^Y16 are a hydrogen atom or a substituent. However, it is not necessary for all of R ^Y7 to R ^Y9 to be hydrogen atoms. It is preferable that the substituent is an organic group (C1-36 is preferable, 1-24 are more preferable, and 1-12 are more preferable), it may interpose a coupling group L, and may have a substituent T. Carbonization It is preferable that it is a hydrogen group. As a hydrocarbon group, the group of R ^Y2 is preferable.

In formula (Y1-2), R ^Y7 and R ^Y8 are carboxyalkyl groups (C 1-12 are preferable, 1-6 are more preferable, 1-3 are still more preferable; the number of carboxyl groups is 1-12 is preferable, 1-6 are more preferable, and 1-3 are more preferable) is preferable. An aromatic group is preferable and, as for R ^Y9 , an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are still more preferable). Alternatively, an alkoxycarbonyl group substituted by an aromatic group is preferable (the alkoxyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms, and the aromatic group preferably has 6 to 22 carbon atoms, 6-18 are more preferable, and 6-14 are more preferable).

In another preferable aspect of Formula (Y1-2), R ^Y7 and R ^Y8 are alkyl groups (C1-C12 are preferable, 1-6 are more preferable, and 1-3 are still more preferable). R ^Y9 is preferably a group having an aromatic group (C6-C22 is preferable, more preferably 6-18, further preferably 6-10), and is preferably an alkoxycarbonyl group having an aromatic group.

In formula (Y1-3), it is preferable that R ^Y11 and R ^Y13 are a hydrogen atom. Two of R ^Y14 and R ^Y15 may be combined to form a substituent in the form of =C(NR ^N ₂ ) ₂ (= means bonding to a nitrogen atom by a double bond).

In the formula (Y1-4), R ^Y13 is preferably a hydrogen atom, R ^Y10 , R ^Y11 , R ^Y12 , R ^Y16 is an alkyl group (C 1 to 12 are preferable, 1 to 6 are more preferable, 1 ~3 is more preferred). At this time, it is preferable that R ^Y11 and R ^Y16 , and R ^Y10 and R ^Y12 combine to form a ring to form a bicyclo compound. Specific examples thereof include diazabicyclononene and diazabicycloundecene.

In this embodiment, it is preferable that the carboxylate anion paired with the quaternary ammonium cation of the said formula (Y1-1), a formula (Y1-3), and a formula (Y1-4) is represented by a following formula (X1) .

[Formula 20]

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

The electron withdrawing group in this embodiment means that Hammett's substituent constant (sigma)m shows a positive value. Here, σm is, Editorial by Yuho Tsuno, Journal of the Association of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) p. 631-642 are described in detail. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said document.

Examples of the substituent in which σm is positive include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group (σm=0.06) , Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), and the like. . In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

It is preferable that EWG is group represented by following formula (EWG-1) - (EWG-6).

[Formula 21]

In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 are each independently a hydrogen atom or an alkyl group (C1-C12 is preferable, 1-6 are more preferable, 1-3 are more preferably), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms) and 6-10 are more preferable), a hydroxyl group, or a carboxyl group. Ar represents an aromatic group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are still more preferable). When R ^x1 to R ^x3 are an alkyl group, an alkenyl group or an aryl group, a ring may be formed. These alkyl group, alkenyl group, aryl group, and Ar may have the substituent T in the range which does not impair the effect of this invention. Especially, it is preferable that Ar has a carboxyl group (preferably 1-3 pieces) especially. * indicates a binding position.

L ¹ is a group having the same meaning as the linking group L, and is preferably -CR ^X2 R ^X3 -, -Ar ¹ -, or a group combining these. Ar ¹ is an arylene group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are still more preferable).

Np represents the integer of 1-6, the integer of 1-3 is preferable, and 1 or 2 is more preferable.

The molecular weight of a thermosetting accelerator becomes like this. Preferably it is 100 or more and less than 2000, More preferably, it is 200-1000.

As a specific example of the thermosetting accelerator, an acidic compound that generates a base when heated to 40° C. or higher described in International Publication No. 2015/199219 described in International Publication No. 2015/199219 and an ammonium salt having an anion and ammonium cation having a pKa1 of 0 to 4 are exemplified, and these contents is incorporated herein by reference.

When using a thermosetting accelerator, it is preferable that content of the thermosetting accelerator in a composition is 0.01-50 mass % with respect to the total solid of a composition. 0.05 mass % or more is more preferable, and, as for a minimum, 0.1 mass % or more is still more preferable. As for an upper limit, 10 mass % or less is more preferable, and 5 mass % or less is still more preferable.

As a thermosetting accelerator, 1 type(s) or 2 or more types can be used. When using 2 or more types, it is preferable that a total amount is the said range. Moreover, the composition for film formation can also be set as the structure which does not contain a thermosetting accelerator substantially. Not containing substantially means less than 0.01 mass % with respect to the total solid of a composition, and it is more preferable that it is less than 0.005 mass %.

<<Photocuring accelerator>>

The composition for film formation may contain the photocuring accelerator. The photocuring accelerator is preferably one that generates a base upon exposure, and does not show activity under normal conditions of room temperature and normal pressure, but generates a base (basic substance) when irradiation and heating of electromagnetic waves as an external stimulus are performed. It is preferable that Since the base generated by exposure acts as a catalyst at the time of hardening a polyimide precursor by heating, it can use suitably. Preferred conditions for exposure are the same as those defined in the following exposure process.

A well-known thing can be used as a photocuring accelerator. For example, a transition metal compound complex, an ionic compound having a structure such as an ammonium salt, or an ionic compound neutralized by a base component forming a salt, such as an amidine moiety latent by forming a salt with a carboxylic acid, or a carbamate derivative and a nonionic compound in which a base component is latent by a urethane bond or an oxime bond, such as an oxime ester derivative and an acyl compound.

As a photocuring accelerator, the photocuring accelerator which has a cinnamic acid amide structure as disclosed in Unexamined-Japanese-Patent No. 2009-080452 and International Publication No. 2009/123122, Unexamined-Japanese-Patent No. 2006-189591, and Unexamined-Japanese-Patent No. A photocuring accelerator having a carbamate structure as disclosed in Patent Publication No. 2008-247747, an oxime structure as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581, a photocuring accelerator having a carbamoyloxime structure Although a photocuring accelerator etc. are mentioned, It is not limited to these, In addition, the structure of a well-known photocuring accelerator can be used.

In addition, as a photocuring accelerator, Paragraph 0185 - 0188 of Unexamined-Japanese-Patent No. 2012-093746, the compound of 0199 - 0200, and 0202 The compound of Paragraph 0022 - 0069 of Unexamined-Japanese-Patent No. 2013-194205, Unexamined-Japanese-Patent No. The compound of Paragraph 0026 - 0074 of 2013-204019, and the compound of Paragraph 0052 of International Publication No. 2010/064631 are mentioned as an example.

Commercially available photocuring accelerators include 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 Junyaku Co., Ltd.) can also be used.

When using a photocuring accelerator, it is preferable that content of the photocuring accelerator in a composition is 0.1-50 mass % with respect to the total solid of a composition. As for a minimum, 0.5 mass % or more is more preferable, and 1 mass % or more is still more preferable. 30 mass % or less is more preferable, and, as for an upper limit, 20 mass % or less is still more preferable.

One type or two or more types can be used for a photocuring accelerator. When using 2 or more types, it is preferable that a total amount is the said range.

<Other additives>

The composition for film formation may contain, as needed, various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant other than those described above, a higher fatty acid derivative, An inorganic particle, a hardening|curing agent, a curing catalyst, a filler, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. can be mix|blended. When mix|blending these additives, it is preferable that the total compounding quantity shall be 3 mass % or less of solid content of a composition.

<<Thermal acid generator>>

The composition for film formation may contain the thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the film. As a thermal acid generator, the compound etc. of Paragraph 0059 of Unexamined-Japanese-Patent No. 2013-167742 are mentioned. A preferable range of the heating temperature (acid generation temperature) of the thermal acid generator is the same as the temperature specified in the following heating step.

0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. Since the crosslinking reaction and cyclization of a polyimide precursor are accelerated|stimulated by containing 0.01 mass part or more of a thermal acid generator, the mechanical property and chemical-resistance of a film|membrane can be improved more. Moreover, 20 mass parts or less are preferable from a viewpoint of the electrical insulation of a film|membrane, as for content of a thermal acid generator, 15 mass parts or less are more preferable, and its 10 mass parts or less are still more preferable.

Only 1 type may be used for a thermal acid generator, and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<sensitizing dye>>

The film-forming composition may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and becomes an electron excited state. The sensitizing dye used in the electron excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects, such as electron transfer, energy transfer, and heat_generation|fever, generate|occur|produce. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator cause a chemical change, are decomposed, and generate a radical, an acid or a base. About the detail of a sensitizing dye, Paragraph 0161 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0163 can be considered into consideration, and this content is integrated in this specification.

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

<<Chain Transfer Agent>>

The composition for film formation may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary 3rd Edition (Edited by the Society of Polymers, 2005). As a chain transfer agent, the compound group which has SH, PH, SiH, and GeH in a molecule|numerator is used, for example. These can generate a radical by donating hydrogen to a radical with low activity to generate a radical, or by deprotonation after being oxidized. In particular, thiol compounds (eg, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) etc.) can be preferably used.

When the composition for film formation has a chain transfer agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of total solids of the composition for film formation, as for content of a chain transfer agent, 1-10 mass parts is more preferable, 1-5 A mass part is more preferable. Only 1 type may be sufficient as a chain transfer agent, and 2 or more types may be sufficient as it. When 2 or more types of chain transfer agents are, it is preferable that the sum total is the said range.

<<Higher Fatty Acid Derivatives>>

In the film-forming composition, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent oxygen-induced polymerization inhibition, and may be localized on the surface of the composition during drying after application.

When the composition for film formation has a higher fatty acid derivative, it is preferable that content of a higher fatty acid derivative is 0.1-10 mass % with respect to the total solid of the composition for film formation. The number of higher fatty acid derivatives may be one, and 2 or more types may be sufficient as them. When there are two or more types of higher fatty acid derivatives, it is preferable that the sum total is the said range.

<Restrictions on other contained substances>

From the viewpoint of coating surface properties, the moisture content of the film-forming composition is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.

From an insulating viewpoint, less than 5 mass ppm (parts per million) is preferable, as for metal content of the composition for film formation, less than 1 mass ppm is more preferable, and its less than 0.5 mass ppm is still more preferable. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When two or more metals are included, it is preferable that the sum total of these metals is the said range.

In addition, as a method of reducing the metallic impurities unintentionally contained in the film-forming composition, a raw material with a small metal content is selected as a raw material constituting the film-forming composition, or the raw material constituting the film-forming composition is filtered through filter. or a method such as performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

From a viewpoint of wiring corrosiveness, content of the halogen atom of the composition for film formation is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm. Especially, less than 5 mass ppm is preferable, as for what exists in a halogen ion state, less than 1 mass ppm is more preferable, and its less than 0.5 mass ppm is still more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom or a chlorine ion and a bromine ion is each in the said range.

As the container for the film-forming composition, a conventionally known container can be used. In addition, for the purpose of suppressing the mixing of impurities into the raw material and composition, as the container for storage, a multi-layer bottle with the inner wall of the container composed of six types and six layers of resin, or a bottle with a seven-layer structure of six types of resins, is also used. desirable. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation of composition>

The composition for film formation can be prepared by mixing the said respective components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Moreover, in order to remove foreign substances, such as dust and microparticles|fine-particles in a composition, it is preferable to perform filtration using a filter. 1 micrometer or less is preferable, as for a filter pore diameter, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. As a filter, you may use what was previously wash|cleaned with the organic solvent. In a filter filtration process, you may connect and use several types of filters in series or parallel. When using multiple types of filters, you may use combining filters from which a pore diameter or a material differs. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may filter by pressurizing. When performing filtration by pressurizing, as for the pressure to pressurize, 0.05 Mpa or more and 0.3 Mpa or less are preferable.

In addition to the filtration using a filter, you may perform the removal process of the impurity using the adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Each process>

It is preferable that the manufacturing method of this invention sets it as the aspect which has the exposure process of exposing after the film-forming process, and the developing process of developing with respect to the exposed film|membrane. After this development, the exposed film can be further cured by heating.

In addition, in order to obtain a laminate, according to the film production method described above, after the film is formed, the film formation process and heating process, the film formation process, the exposure process, and the developing process (additional heating process if necessary) are performed again. , it is preferable to perform in the above order. In particular, it is preferable to perform each of the above steps in order a plurality of times (preferably 2 to 5 times, that is, 3 to 6 times in total). By laminating the films in this way, it is possible to obtain a laminate laminated a desired number of times. When setting it as a laminated body, it is also preferable to apply a metal layer.

<<Film forming process>>

In the manufacturing method of this invention, as mentioned above, it is preferable to include the film-forming process of applying the composition for film-forming to a board|substrate and making it into a film|membrane.

The type of substrate can be appropriately determined depending on the application, but semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, Ni , Cu, Cr, Fe, etc. metal substrate, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, electrode plate of a plasma display panel (PDP), etc. are not particularly limited. However, in this invention, a board|substrate is a member (for example, the board|substrate in which the metal layer was provided) which contains a metal in at least one part. In this invention, the planar shape of the above-mentioned resin film can be made favorable by applying the composition for film formation to a metal surface with a slit coat. Moreover, it is preferable that it is a rectangle, and, as for the shape of a board|substrate, it is more preferable that it is a rectangle.

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

It is preferable that the slit width of a nozzle is 20 micrometers or more, It is more preferable that it is 50 micrometers or more, It is more preferable that it is 80 micrometers or more. As an upper limit, it is preferable that it is 250 micrometers or less, It is more preferable that it is 200 micrometers or less, It is more preferable that it is 150 micrometers or less.

It is preferable that a slit gap is 30 micrometers or more, It is more preferable that it is 50 micrometers or more, It is more preferable that it is 70 micrometers or more. As an upper limit, it is preferable that it is 200 micrometers or less, It is more preferable that it is 150 micrometers or less, It is more preferable that it is 120 micrometers or less.

1 mm/s or more may be sufficient as a scan speed, It is preferable that it is 10 mm/s or more, It is more preferable that it is 20 mm/s or more, It is more preferable that it is 30 mm/s or more. As an upper limit, it is preferable that it is 500 mm/s or less, It is more preferable that it is 400 mm/s or less, It is more preferable that it is 300 mm/s or less.

It is preferable that the coating film thickness is 1 micrometer or more, It is more preferable that it is 2 micrometers or more, It is more preferable that it is 3 micrometers or more. As an upper limit, it is preferable that it is 100 micrometers or less, It is more preferable that it is 80 micrometers or less, It is more preferable that it is 50 micrometers or less.

<<Drying process>>

In the manufacturing method of this invention, you may include the process of drying in order to remove a solvent after formation of a film|membrane. A preferable drying temperature is 50-150 degreeC, 70 degreeC - 130 degreeC are more preferable, and 90 degreeC - 110 degreeC are still more preferable. As drying time, 30 second - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 3 minutes - 7 minutes are more preferable.

The film thickness of the dried film can be, for example, 0.5 µm or more, or 1 µm or more. Moreover, as an upper limit, it can be set as 100 micrometers or less, and can also be set as 30 micrometers or less. This thickness is the same also in the film thickness after the following heating process.

<<Exposure process>>

It is preferable to irradiate 100-10000 mJ/cm< ² > in conversion of exposure energy in wavelength 365nm, for example, and, as for the exposure amount in an exposure process, it is more preferable to irradiate 200-8000 mJ/cm< ² >.

An exposure wavelength can be suitably determined in the range of 190-1000 nm, and 240-550 nm is preferable.

The exposure wavelength is, in relation to the light source, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, and i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, etc. are mentioned. About the composition for film formation of this invention, especially exposure by a high-pressure mercury-vapor lamp is preferable, and especially, exposure by i line|wire is preferable. Thereby, particularly high exposure sensitivity can be obtained.

<<Development process>>

The developing method in the developing step is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as paddle, spray, immersion, and ultrasonic waves are employable.

It is preferable to perform image development using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (unexposed portion) is removed. It is preferable that a developing solution contains an organic solvent. In this invention, it is preferable that ClogP value contains the organic solvent of -1-5, and, as for a developing solution, it is more preferable that ClogP value contains the organic solvent of 0-3. A ClogP value can be calculated|required as a calculated value by inputting a structural formula in ChemBioDraw.

The organic solvent is an ester, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate) , ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) For example, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy propionate ethyl, etc.)), 2-alkyloxypropionic acid alkyl esters (eg 2-alkyloxy Methyl propionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2-methylpropionate ethyl (e.g. 2-methoxy-2-methylpropionate methyl, 2-ethoxy -2-methylpropionate etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers, such as di Ethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether As acetate, propylene glycol monopropyl ether acetate, etc., and ketones, for example, methyl ethyl ketone, cyclohexanone, As clopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons, for example, as sulfoxides such as toluene, xylene, anisole, limonene, etc. Dimethyl sulfoxide is preferably mentioned.

In this invention, especially cyclopentanone and (gamma)-butyrolactone are preferable, and cyclopentanone is more preferable.

It is preferable that 50 mass % or more of a developing solution is an organic solvent, It is more preferable that 70 mass % or more is an organic solvent, It is more preferable that 90 mass % or more is an organic solvent. Moreover, 100 mass % of an organic solvent may be sufficient as a developing solution.

As image development time, 10 second - 5 minutes are preferable. Although the temperature at the time of image development is not specifically defined, Usually, it can carry out at 20-40 degreeC.

After the treatment using the developer, rinsing may be further performed. It is preferable to perform rinsing with the solvent different from a developing solution. For example, it can be rinsed using the solvent contained in the composition for film formation. As for rinsing time, 5 second - 1 minute are preferable.

<<Heating process>>

In a heating process, the cyclization reaction of a polyimide precursor advances. As heating temperature (maximum heating temperature) in a heating process, 50-500 degreeC is preferable, 80-450 degreeC is more preferable, 140-400 degreeC is still more preferable, 160-350 degreeC is still more preferable.

It is preferable to perform heating at the temperature increase rate of 1-12 degreeC/min from the temperature at the time of a heating start to a maximum heating temperature, 2-10 degreeC/min is more preferable, 3-10 degreeC/min is still more preferable. By setting the temperature increase rate to 2°C/min or more, excessive volatilization of the amine can be prevented while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the film can be relieved.

20 degreeC - 150 degreeC are preferable, as for the temperature at the time of a heating start, 20 degreeC - 130 degreeC are more preferable, and 25 degreeC - 120 degreeC are still more preferable. The temperature at the time of heating start means the temperature at the time of starting the process of heating to the highest heating temperature. For example, when the film-forming composition is applied on a substrate and then dried, it is the temperature after this drying, for example, the boiling point of the solvent contained in the film-forming composition is gradually increased from a temperature 30 to 200 ° C. lower it is preferable

It is preferable that it is 10-360 minutes, as for heating time (heating time at maximum heating temperature), it is more preferable that it is 20-300 minutes, It is more preferable that it is 30-240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the film, the heating temperature is preferably heated at 180°C to 320°C, more preferably at 180°C to 260°C. Although the reason is not clear, by setting it as this temperature, it is thought that it is because the ethynyl groups of an interlayer polyimide precursor are advancing a crosslinking reaction.

Heating may be performed in stages. For example, a pretreatment process such as raising the temperature from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, increasing the temperature from 180°C to 200°C at 2°C/min, and holding at 200°C for 120 minutes may be done 100-200 degreeC is preferable, as for the heating temperature as a pretreatment process, it is more preferable that it is 110-190 degreeC, It is more preferable that it is 120-185 degreeC. In this pretreatment process, it is also preferable to process while irradiating an ultraviolet-ray as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in the short time of about 10 second - 2 hours, and 15 second - 30 minutes are more preferable. A pretreatment is good also as two or more steps, for example, may perform the pretreatment process 1 in the range of 100-150 degreeC, and may perform the pretreatment process 2 in the range of 150-200 degreeC after that.

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

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

<<Metal layer forming process>>

You may apply and form a metal layer to the surface of the film|membrane of the film-forming composition after development.

The metal layer is not particularly limited, and an existing metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, with copper and aluminum being more preferable, and copper being more preferable. .

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the method of Unexamined-Japanese-Patent No. 2007-157879, Unexamined-Japanese-Patent No. 2001-521288, Unexamined-Japanese-Patent No. 2004-214501, and Unexamined-Japanese-Patent No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, the patterning method which combined sputtering, photolithography, and etching, and the patterning method which combined photolithography and electroplating are mentioned.

As thickness of a metal layer, 0.1-50 micrometers is preferable in the thickest part, and 1-10 micrometers is more preferable.

<<Lamination process>>

The lamination step may include again performing the above-mentioned film-forming step and heating step, or the film-forming step, the above-mentioned exposure step, and the above-mentioned developing step, in the above order on the surface of the film or metal layer of the film-forming composition. The lamination step may further include the drying step, the heating step, and the like.

When performing a lamination|stacking process further after a lamination process, you may perform a surface activation treatment process further after the said heating process, after the said exposure process, or after the said metal layer formation process. Plasma treatment is exemplified as the surface activation treatment.

It is preferable to perform 2-5 times, and, as for the said lamination|stacking process, it is more preferable to perform 3-5 times.

For example, a structure in which the resin layer is 3 or more and 7 or less layers, such as a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferable, and 3 or more layers and 5 layers or less are more preferable.

That is, after providing the metal layer, in the film formation step and heating step of the composition for film formation, or the composition for film formation, the film formation step, the exposure step, and the developing step (required It is preferable to further perform a heating step) in the above order. By alternately performing the lamination process of laminating the film (resin) of the composition for film formation, and the metal film formation process, the film|membrane (resin layer) and the metal layer of the composition for film formation can be laminated|stacked alternately.

As a specific example of a semiconductor device in which the film of the film-forming composition obtained by the production method of the present invention is used to form an interlayer insulating film for a redistribution layer, reference may be made to the description in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and the description in FIG. 1 . and these contents are incorporated herein by reference.

The present invention also discloses a method for manufacturing a semiconductor device in which a chip is disposed on the film of the present invention. Also disclosed is a method for manufacturing a semiconductor device in which a chip is disposed in the laminate of the present invention. Regarding the chip and the chip arrangement method here, reference can be made to the description of the semiconductor three-dimensional packaging technology, Seiichi Denda, and CQ Shukpansha, published on June 1, 2011, the contents of which are incorporated herein by reference.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. Materials, usage amounts, ratios, treatment details, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are by mass unless otherwise specified.

<Synthesis Example 1>

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

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were suspended in 50 mL of N-methylpyrrolidone, It was dried with a molecular sieve. The suspension was heated at 100° C. for 3 hours. A clear solution was obtained after a few minutes after heating. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) pyridine and 90 mL N-methylpyrrolidone were added. The reaction mixture was then cooled to −10° C. and 16.12 g (135.5 mmol) thionyl chloride was added over 10 minutes while maintaining the temperature at −10±4° C. While adding 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 obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23°C for 20 minutes. The reaction mixture was then stirred at room temperature overnight. Then, the polyimide precursor resin was precipitated in 5 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 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. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 degreeC for 3 days. This polyimide precursor was Mw=22800 and Mn=8100.

<Synthesis Example 2>

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

20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a flat bottom joint equipped with a stirrer, a condenser and an internal thermometer. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridines were added successively, and it stirred at the temperature of 60 degreeC for 18 hours. Then, after cooling the mixture 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 warmed to room temperature and stirred for 2 hours, then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Then, to the obtained transparent liquid, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour. During the addition of 4,4'-diaminodiphenylether, 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. Then, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again for 30 minutes in 4 liters of water, followed by filtration. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 degreeC for 3 days. This polyimide precursor was Mw=23500 and Mn=8800.

<Synthesis Example 3>

[Polyimide precursor resin from oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenylether Synthesis of A-3]

10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride while removing moisture in a dry reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer 9.47 g (32.3 mmol) were suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridines were added successively, and it stirred at the temperature of 60 degreeC for 18 hours. Then, after cooling the mixture 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 warmed to room temperature and stirred for 2 hours, then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Then, to the obtained transparent liquid, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour. During the addition of 4,4'-diaminodiphenylether, 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. Then, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again for 30 minutes in 4 liters of water, followed by filtration. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 degreeC for 3 days. This polyimide precursor was Mw=24300 and Mn=9500.

<Preparation of the composition for film formation>

The composition for film formation of each Example and the comparative example was prepared as a uniform solution by mix|blending in the ratio (part by mass) shown in the following table|surface. In the example mentioned later, the obtained composition was filtered using the polyethylene filter which has a pore size of 0.8 micrometer, and was used.

<Film formation by slit coat>

As a board|substrate, the board|substrate which formed the copper film of 100 nm thickness into a film by sputtering on the surface of the 150 mm horizontal, 150 mm length, and thickness 0.7mm alkali-free-glass board|substrate was prepared. A coating film of the composition for film formation prepared above was formed on the surface of this substrate using a slit coater (SCREEN Finetec Solutions, LC-R300G, provided with a slit head width of 100 mm and a coating length of 100 mm). The detailed conditions of the device of the slit coater are as shown in the table below. This was left to stand for 5 minutes at 23 degreeC and reduced pressure 50 Pa, and it dried on the conditions of leaving it to stand at 100 degreeC for 5 minutes on a hotplate. The coating film thickness (after drying) was measured at 10 mm intervals from the position of 10 mm from the edge part of the application part using the F20 film thickness measurement system made by Film Matrix, and the average value was taken. At the time of film forming, in a head standby process, the nozzle head was immersed in the immersion liquid under the conditions shown in the following table|surface. Moreover, the nozzle head was immersed in the washing|cleaning liquid in the head washing|cleaning process after film forming. The temperature at the time of immersion and washing|cleaning was made into (normal temperature (23 degreeC)).

<Applicability>

The applicability at the time of the said slit coating was evaluated. The coating film formed on the substrate was left to stand for 5 minutes at 23° C. and reduced pressure of 50 Pa, dried on a hot plate 100° C. for 5 minutes under conditions of standing, and then visually observed to confirm whether lumps or streaks were observed. The observation area was made into the whole surface except 10 mm from the cross section of the application part. In each Example and Comparative Example, the average value of three samples was employ|adopted.

Little or no clumps or streaks, and uniform: good

Slight lumps or streaks were observed, but mostly uniform: positive

Lots of clumps or streaks: below standard

<Face after application and drying>

It evaluated about the surface after application-drying at the time of the said slit coating. The coating film (after drying) formed into a film on the board|substrate was observed visually, and the surface shape was confirmed from the reflection state of a fluorescent lamp. In each Example and Comparative Example, the average value of three samples was employ|adopted.

Fluorescent lamp is reflected as it is in the entire application area - Gloss: Excellent

At least part of the applicator has a dimly visible fluorescent light-slightly orange peel: positive

Fluorescent light dims over the entire surface of the application area - Orange peel: below standard

<In-plane uniformity after application and drying>

In-plane uniformity of the film thickness after application|coating and drying at the time of the said slit coating was evaluated. The film thickness distribution of the coating film on the surface of the substrate on which the coating film (after drying) was applied was measured by a film thickness measuring device (manufactured by Film Matrix, F20 film thickness measurement system), excluding the 10 mm at the end of the coated part, 90 mm long and 90 mm wide. 81 points were measured at intervals of 10 mm, and the maximum and minimum difference was taken as TTV (Total thickness variation). In each Example and Comparative Example, the average value of three samples was employ|adopted.

TTV was measured in the area|region except 10 mm from the application|coating part edge part.

≤1μm: good

>1μm, ≤2μm: positive

>2μm: substandard

<Drying time after application>

Said drying process WHEREIN: After mounting on a hotplate, time until drying was evaluated. When the surface of the application part was brought into contact with a cotton swab at the elapsed time of the specified time, if marks remained, drying was not completed, and if no marks were left, drying was completed. In each Example and Comparative Example, the average value of three samples was employ|adopted. In addition, the measurement was made into the drying time in 100 degreeC.

≤300sec: Excellent

>300sec, ≤400: quantity

>400sec: less than standard

<Nozzle head contamination after nozzle head cleaning>

In the above film forming step, the cleaning liquid having the composition shown in the table is put into the bat, the nozzle head is immersed at 23 ° C. for the time shown in the table, so that the slit of the nozzle head is immersed in the cleaning liquid, and the nozzle head after cleaning the nozzle head contamination was assessed. In each Example and the comparative example, it employ|adopted in 3 tests. In addition, the measurement was made into the drying time in 100 degreeC.

No contamination was confirmed in all 3 times: none

Contamination confirmed at least 1 out of 3 times: Yes

<Adhesiveness to members of the coating film (shear test)>

The shear test was implemented about the coating film after drying of the film|membrane formed by the said slit coat on the various board|substrates of Tables 1-9. The measuring apparatus (made by XYZTEC, Condor Sigma bond tester) was used. In the test, the dried film after application on the substrate was exposed at an exposure dose of 400 mJ/cm ² using a negative photomask capable of irradiating a 100 μm square pattern, and after 30 minutes, the film after exposure was developed with cyclopentanone, By rinsing with PGMEA, a 100 µm-square film was formed, and the film was pressed from the side at 10 µm/s (needle set at a position of 5 µm from the lower extremity) in the form of pressing. In each Example and Comparative Example, the average value of three samples was employ|adopted.

<10g: less than standard

≥10g, <40g: quantity

≥40g: superior

The same shear test was performed with the Cu plating board|substrate with a coating film, Al-Si-Cu alloy plating board|substrate, Ti sputtering board|substrate, and Ni sputtering board|substrate. In addition, about Examples 32-36, the same shear test was performed also with the Si substrate to which the coating film was affixed. The evaluation criteria are the same.

<Moisture resistance>

Moreover, PCT (pressure cooker test) was performed about the Cu plating board|substrate and Ti sputtering board|substrate to which the coating film was stuck. The PCT test apparatus (made by SPEC Co., Ltd., EHS-412M) was used. The treatment conditions of the coating film were 121°C, 100% relative humidity (RH), and 500 hours. About the coating film after a process, adhesive evaluation (shear test) was performed on the conditions similar to the test of the said <Adhesiveness to member of a coating film>. The evaluation criteria are the same.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

sec: seconds, min: minutes

*1 Immersion: Head Standby Immersion: Immersion for 30 seconds after application, Discharge after 30 seconds after immersion

*2 Comparative Example 2: ※If DMSO is 100%, it cannot be dried by absorbing moisture in the air.

Poor dissolution: could not be applied because the solids did not dissolve in the solvent

Impossible to measure: could not be measured because it could not be applied

Impossible to do: Adhesion test could not be done because it could not be applied

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

Surfactant (Megapac [brand name], DIC)

Water solubility expressed the quantity (g) melt|dissolved in 100 g of 23 degreeC water in unit and mass %. Molecular weight is a weight average molecular weight.

[Table 10]

(C) photoradical polymerization initiator

C-1: BASF Corporation, IRGACURE OXE-01

C-2: the following compound

[Formula 22]

(D) radically polymerizable compound

D-1: Shin-Nakamura Kagaku High School, NK Ester A-9300

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

(E) polymerization inhibitor

E-1: Parabenzoquinone (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

E-2: 4-methoxyphenol

(F) Migration inhibitor (rust inhibitor)

F-2: 1H-tetrazole

(G) metal adhesion improving agent (silane coupling agent)

G-1: Made by Shin-Etsu Chemical High School, part number: KBM-602

G-2: the following compound (wherein Et represents an ethyl group)

[Formula 23]

(H) curing accelerator (thermal base generator)

H-1: the following compound

[Formula 24]

H-2: the following compound

[Formula 25]

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

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

<Example in which exposure and development were performed>

The composition for film formation produced in Example 1 was apply|coated on the copper wafer (corresponding to a metal layer and a member containing a metal) by a slit coat, and the coating film was formed. The obtained coating film was dried at 100 degreeC for 5 minutes on a hotplate, and the uniform precured film (film|membrane of the composition for film formation) with a thickness of about 15 micrometers was obtained. This was exposed through a mask having a line-and-space pattern (step: 5 to 20 µm) using an aligner (Karl-Suss MA150 [trade name]). Exposure was performed with a high pressure mercury lamp, and 500 mJ/cm< ² > was irradiated in conversion of the exposure energy in wavelength 365nm.

The precured film after exposure was melt|dissolved for 75 second with cyclopentanone, and puddle development was carried out. The line width of the developed site was evaluated on the basis of the following criteria. The exposure width of the base substrate after image development was less than +/-10% with respect to the mask size, and it confirmed that favorable exposure development was possible.

The formed resin pattern was heated at 250°C for 3 hours, and the polyimide precursor was subjected to a cyclization reaction to obtain a polyimide resin, thereby obtaining a resin pattern with extremely stable and strength while being a fine pattern.

Since the produced resin pattern is composed of polyimide, it has excellent insulating properties, has good compatibility with metals as described above, and can appropriately respond to fine processing, so WL-CSP (Wafer Level Chip Size Package) ) was found to be particularly suitable for the production of a redistribution layer.

In Example 1, polyimide precursor A-1 was changed into polyimide precursor A-2 or A-3, and it carried out similarly to the other thing. As in Example 1, an excellent effect was obtained. On the other hand, in the comparative example 1, polyimide precursor A-1 was changed into polyimide precursor A-2 or A-3, and it performed similarly to the other thing. Similar to Comparative Example 1, the flat surface after application and drying was inferior.

21 nozzle head
22 Nozzle Head Cleaner
23 Carrier
21a resin
24 rollers
25 roller bat
25b liquid cutting blade
25a cleaning solution
26 Maintenance Department
100 slit coat device

Claims (23)

a polyimide precursor;
At least two solvents having different solubility in the polyimide precursor at 23°C;
Using a composition comprising at least one selected from the group consisting of a plasticizer and a compound having a weight average molecular weight of 5,000 or less, and a surfactant that dissolves 0.1% by mass or more in water at 23°C,
A method for producing a film, comprising the step of performing a slit coat on a member, wherein the member contains a metal at least in part thereof. The method according to claim 1,
The method for producing a film, wherein the surfactant contains a perfluoroalkyl group. The method according to claim 1 or 2,
A method for producing a film, comprising: a head cleaning step of cleaning a nozzle head with a cleaning solution after the step of performing slit coating. 4. The method of claim 3,
In the step of performing the slit coating, a head waiting step is included, wherein in the head waiting step, the nozzle head is immersed in an immersion liquid, wherein the immersion liquid is a liquid having a composition common to the cleaning liquid by 90% by mass or more. , a method of manufacturing the membrane. 4. The method of claim 3,
The said washing|cleaning liquid contains the solvent with the highest solubility in 23 degreeC of the said polyimide precursor among the said at least 2 types of solvents, The manufacturing method of a film|membrane. 4. The method of claim 3,
The said washing|cleaning liquid contains the solvent with the lowest solubility in 23 degreeC of the said polyimide precursor among the said at least 2 types of solvents, The manufacturing method of a film|membrane. 5. The method according to claim 4,
The said immersion liquid contains the solvent with the highest solubility in 23 degreeC of the said polyimide precursor among the said at least 2 types of solvent, The manufacturing method of a film|membrane. 5. The method according to claim 4,
The said immersion liquid contains the solvent with the lowest solubility in 23 degreeC of the said polyimide precursor among the said at least 2 types of solvents, The manufacturing method of a film|membrane. The method according to claim 1 or 2,
A method for producing a film, comprising: an exposure step of exposing the film formed by the slit coat; and a developing step of developing the exposed film. The method according to claim 1 or 2,
A method for producing a film, further comprising a heating step of heating the film. The manufacturing method of the laminated body which performs the manufacturing method of the film|membrane of Claim 1 or 2 multiple times. 12. The method of claim 11,
and applying a metal layer to the film. A method for manufacturing a semiconductor device in which a chip is disposed on a film manufactured by the method according to claim 1 or 2. A method for manufacturing a semiconductor device in which a chip is disposed on a laminate manufactured by the method according to claim 11 . It is a composition for film formation used by the manufacturing method of Claim 1 or 2, Comprising: A polyimide precursor, at least 2 types of solvent from which the solubility in 23 degreeC with respect to the said polyimide precursor differs, a plasticizer, and a weight average molecular weight 5,000 A film-forming composition comprising the following compounds, and at least one selected from the group consisting of surfactants soluble in water at 23°C in an amount of 0.1% by mass or more. 16. The method of claim 15,
The composition for film formation wherein the polyimide precursor is a condensate of dicarboxylic acid or a dicarboxylic acid derivative and diamine. 16. The method of claim 15,
Among the at least two solvents, the solvent having the highest solubility of the polyimide precursor is a sulfoxide solvent, and among the at least two solvents, the solvent having the lowest solubility of the polyimide precursor is a ketone or lactone. A solvent, a film-forming composition. 16. The method of claim 15,
A ratio of the total mass of the solvent having a solubility of the polyimide precursor higher than the following average value among the at least two solvents and the total mass of the solvent having a solubility of the polyimide precursor lower than the following average value among the at least two solvents This 10:90-45:55 composition for film formation;
The said average value is the average value of the solubility of the solvent with the highest solubility in 23 degreeC of a polyimide precursor, and the solubility of the lowest solvent in 23 degreeC of a polyimide precursor. 16. The method of claim 15,
The composition for film formation, wherein the surfactant contains a fluorine atom. 20. The method of claim 19,
The surfactant comprises a perfluoroalkyl group, the composition for film formation. 16. The method of claim 15,
The content of the said surfactant is 0.005-2 mass % in solid content, The composition for film formation. 16. The method of claim 15,
wherein the plasticizer is an epoxidized oil. 16. The method of claim 15,
The content of the said plasticizer is 0.005-2 mass % in solid content, The composition for film formation.

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