CN113474156B

CN113474156B - Polyamic acid resin composition, polyimide resin film and method for producing same, laminate, and electronic device and method for producing same

Info

Publication number: CN113474156B
Application number: CN202080014520.1A
Authority: CN
Inventors: 越野美加; 芦部友树; 宫崎大地
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2019-02-26
Filing date: 2020-02-14
Publication date: 2022-04-29
Anticipated expiration: 2040-02-14
Also published as: JP7127681B2; TWI798530B; JPWO2020175167A1; CN113474156A; TW202033620A; WO2020175167A1; KR20210132030A

Abstract

The present invention addresses the problem of providing a polyamic acid resin composition that can achieve sufficient adhesion to both a support such as glass and an inorganic film such as SiOx used as a gas barrier film, and that can provide a polyimide resin film after firing that has excellent mechanical properties and visible light transmittance. The polyamic acid resin composition comprises (a) polyamic acid and (b) a compound represented by a general formula (1), wherein the polyamic acid (a) is a polyamic acid with a specific repeating unit, and the polyamic acid resin composition is a non-photosensitive resin composition. (in the general formula (1), R¹Represents a hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 1 to 4 carbon atoms, X represents an organic group containing a nitrogen atom, and Y represents a specific group. l is an integer of 0 to 2, when l is 2, a plurality of R¹May be the same or different. N is 0 or 1, k is 1 or 2, and m is an integer of 1 to 3. )

Description

Polyamic acid resin composition, polyimide resin film and method for producing same, laminate, and electronic device and method for producing same

Technical Field

The present invention relates to a polyamic acid resin composition, a polyimide resin film, and an electronic device including the same.

Background

Heat-resistant resins represented by polyimide and the like are used as materials for various electronic devices because of their excellent electrical insulating properties, heat resistance, and mechanical properties. Recently, a flexible display device and a light receiving device resistant to impact can be manufactured by using a heat-resistant resin film for a substrate of a light receiving device such as an organic EL display, a liquid crystal display, an electronic paper, a micro LED, or the like, a scintillator (scintillator), or a solar cell.

The method of manufacturing a flexible device using a polyimide resin film as a substrate includes: a step of forming a polyimide resin film on a support such as a glass substrate, a step of forming a semiconductor such as a TFT (thin film transistor) on the polyimide resin film, and a step of peeling the polyimide resin film from the support. Conventionally, in the formation of a TFT or the like on a polyimide resin film, an inorganic film such as silicon oxide (SiOx), silicon nitride (SiNy), or silicon oxynitride (SiOxNy) is formed as a gas barrier film on the polyimide resin film before the formation of the TFT or the like.

In recent years, a technique has been studied in which a polyimide resin film/an inorganic film/a polyimide resin film/an inorganic film is formed by repeating lamination of a polyimide resin film and an inorganic film, thereby improving reliability of a device. Therefore, the polyimide resin film needs to have appropriate adhesion to the support as follows: the inorganic film is not peeled from the support and the inorganic film during the process, and the inorganic film can be easily peeled from the support by, for example, an excimer laser in the peeling process.

Therefore, as a method for improving the adhesion between the polyimide and the support, for example, the following methods are proposed: a method of adding an alkoxysilane compound having an amide structure as an adhesion improver (for example, see patent documents 1 and 2); a method of introducing an alkoxysilane site to a resin terminal using an aminosilane compound (for example, see patent document 3).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2013/125193

Patent document 2: international publication No. 2016/10003

Patent document 3: international publication No. 2014/123045

Disclosure of Invention

Problems to be solved by the invention

However, in the techniques using a silane coupling agent having an amide structure as disclosed in patent documents 1 and 2, although sufficient adhesion to a glass substrate can be obtained, adhesion to an inorganic film is insufficient. On the other hand, in the technique of introducing an alkoxysilane site to a resin terminal as shown in patent document 3, adhesion to an inorganic film is insufficient as in the case of the techniques shown in patent documents 1 and 2. Further, depending on the type of acid anhydride or diamine used, there are problems of a slow modification reaction and poor productivity.

The purpose of the present invention is to provide a polyamic acid resin composition which can obtain sufficient adhesion to both a support such as glass and an inorganic film such as SiOx used as a gas barrier film, and which can form a polyimide resin film having excellent mechanical properties and visible light transmittance after firing.

Means for solving the problems

The invention is the technical scheme as follows.

[1] The polyamic acid resin composition comprises (a) polyamic acid and (b) a compound represented by a general formula (1), wherein the (a) polyamic acid is a polyamic acid with a repeating unit represented by a general formula (10), and the polyamic acid resin composition is a non-photosensitive resin composition.

[ chemical formula 1]

(in the general formula (10), A represents a 4-valent tetracarboxylic acid residue having 2 or more carbon atoms and has a chemical structure mainly composed of a 4-valent tetracarboxylic acid residue represented by the chemical formula (11) or (12) (hereinafter, the 4-valent tetracarboxylic acid residue is also abbreviated as a tetracarboxylic acid residue.) B represents a 2-valent diamine residue having 2 or more carbon atoms and a chemical structure mainly composed of a 2-valent diamine residue represented by the chemical formula (13) (hereinafter, the 2-valent diamine residue is also abbreviated as a diamine residue.) R¹¹And R¹²Each independently represents a hydrogen atom or a carbon atom of 1 to 10A hydrocarbon group, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion. r is a positive integer. )

[ chemical formula 2]

[ chemical formula 3]

(in the general formula (1), R¹Represents a hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 1 to 4 carbon atoms, X represents an organic group containing a nitrogen atom, and Y represents a group represented by the general formula (2) or (3). L is an integer of 0 to 2, and when L is 2, a plurality of R¹May be the same or different. n is 0 or 1. When k is 1 or 2 and k is 2, a plurality of xs may be the same or different. m is an integer of 1 to 3, and when m is 2 or more, plural Y's may be the same or different. )

[ chemical formula 4]

(in the general formulae (2) and (3), σ represents an oxygen atom or a sulfur atom, R²And R³Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. h and j are each 0 or 1. )

[2] A polyamic acid resin composition comprising (a) a polyamic acid and (b) a compound represented by the general formula (1), wherein a polyimide resin film obtained by applying the polyamic acid resin composition to a support and then firing the composition at 500 ℃ for 30 minutes in an inert gas atmosphere shows an elongation at break of 5 to 150% at a film thickness of 10 [ mu ] m.

Hereinafter, the term "1" will be referred to as a first embodiment, and the term "2" will be referred to as a second embodiment.

Effects of the invention

According to the present invention, a polyamic acid resin composition can be obtained which has high adhesion to a support such as glass and an inorganic film such as SiOx used as a gas barrier film, and which is excellent in mechanical properties and visible light transmittance of a polyimide resin film obtained by firing.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail.

The polyamic acid resin composition according to the first and second embodiments of the present invention includes (a) a polyamic acid and (b) a compound represented by general formula (1).

[ chemical formula 5]

In the general formula (1), R¹Represents a hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 1 to 4 carbon atoms, X represents an organic group containing a nitrogen atom, and Y represents a group represented by the general formula (2) or (3). l is an integer of 0 to 2, when l is 2, a plurality of R¹May be the same or different. n is 0 or 1. When k is 1 or 2 and k is 2, a plurality of xs may be the same or different. m is an integer of 1 to 3, and when m is 2 or more, plural Y's may be the same or different.

[ chemical formula 6]

In the general formulae (2) and (3), σ represents an oxygen atom or a sulfur atom, R²And R³Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. h and j are each 0 or 1.

< (a) Polyamic acid

The polyamic acid (a) is obtained by reacting a diamine with a tetracarboxylic acid, as described later. The polyamic acid can be converted into polyimide as a heat-resistant resin by heating and chemical treatment.

The polyamic acid (a) used in the present invention preferably has a repeating unit represented by the general formula (10).

[ chemical formula 7]

In the general formula (10), A represents a 4-valent tetracarboxylic acid residue having 2 or more carbon atoms, and B represents a 2-valent diamine residue having 2 or more carbon atoms. The tetracarboxylic acid residue as used herein means a partial chemical structure derived from a tetracarboxylic acid, a tetracarboxylic acid dianhydride, a tetracarboxylic acid diester, or the like, and the diamine residue means a partial chemical structure derived from a diamine.

In the general formula (10), R¹¹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion. r is a positive integer.

As described later, r is preferably 5 or more, and more preferably 10 or more. The upper limit of r is not particularly limited, and is usually 1000 or less. When r is 2 or more, a plurality of a in the general formula (10) may be the same or different, and similarly, a plurality of b may be the same or different.

In the general formula (10), A is preferably a C2-80 4-valent hydrocarbon group. A may be a 4-valent organic group having 2 to 80 carbon atoms, which includes 1 or more atoms selected from the group consisting of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen, and which includes hydrogen atoms and carbon atoms as essential constituent atoms.

The tetracarboxylic acid to provide a is not particularly limited, and known ones can be used. Examples thereof include pyromellitic acid, 3,3 ', 4, 4' -biphenyltetracarboxylic acid, 2,3,3 ', 4' -biphenyltetracarboxylic acid, 2 ', 3, 3' -biphenyltetracarboxylic acid, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid, 3,3 ', 4, 4' -diphenylethertetracarboxylic acid, 9-bis (3, 4-dicarboxyphenyl) fluorene, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, cyclobutanetetracarboxylic acid, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,2,4, 5-cyclohexanetetracarboxylic acid, tetracarboxylic acid described in International publication No. 2017/099183, and the like.

From the viewpoint of heat resistance of the polyimide obtained, it is preferable that a is a chemical structure derived from an aromatic tetracarboxylic acid in an amount of 50 mol% or more of the whole a. Among them, A preferably has a chemical structure mainly composed of a 4-valent tetracarboxylic acid residue represented by the chemical formula (11) or (12).

[ chemical formula 8]

That is, it is preferable to use a tetracarboxylic acid residue derived from pyromellitic acid or a tetracarboxylic acid residue derived from 3,3 ', 4, 4' -biphenyltetracarboxylic acid as the main chemical structure of a. The main chemical structure of a as used herein means a structure which accounts for 50 mol% or more of the whole a. More preferably 60 mol% or more, and still more preferably 80 mol% or more. When a polyamic acid resin having a main chemical structure in which the tetracarboxylic acid residue is a is used, a polyimide resin film obtained by firing a polyamic acid resin composition containing the polyamic acid resin has a small coefficient of thermal linear expansion, and can be preferably used as a substrate for a flexible device.

In addition, in order to improve coatability to a support and resistance to oxygen plasma and UV ozone treatment used for cleaning and the like, a tetracarboxylic acid residue derived from a silicon-containing tetracarboxylic acid such as dimethylsilanediphthalic acid or 1, 3-bis (phthalic acid) tetramethyldisiloxane may be contained as a. When the tetracarboxylic acid residue derived from the silicon-containing tetracarboxylic acid is contained, it is preferably contained in a range of 1 to 30 mol% of the whole a.

In the synthesis of the polyamic acid, the tetracarboxylic acids exemplified in the present specification can also be used as they are or in the form of an acid anhydride, an active ester, or an active amide. Among these, acid anhydrides are preferably used because they do not generate by-products in polymerization. In addition, 2 or more of these substances may also be used.

In the general formula (10), B is preferably a 2-valent hydrocarbon group having 2 to 80 carbon atoms. B may be a 2-valent organic group having 2 to 80 carbon atoms, which includes 1 or more atoms selected from the group consisting of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen, and which includes hydrogen atoms and carbon atoms as essential constituent atoms.

The diamine to provide B is not particularly limited, and known ones can be used. Examples thereof include p-phenylenediamine, m-phenylenediamine, 3, 5-diaminobenzoic acid, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfone, 9-bis (4-aminophenyl) fluorene, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 4 ' -diamino-2, 2 ' -bis (trifluoromethyl) diphenyl ether, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-methylphenyl) hexafluoropropane, and, Ethylene diamine, propylene diamine, butylene diamine, cyclohexane diamine, 4' -methylenebis (cyclohexylamine), diamine described in international publication No. 2017/099183, and the like.

From the viewpoint of heat resistance of the polyimide obtained, B is preferably 50 mol% or more of the chemical structure derived from the aromatic diamine based on the whole B. Among them, B is preferably a chemical structure mainly composed of a 2-valent diamine residue represented by the formula (13).

[ chemical formula 9]

That is, the diamine residue derived from p-phenylenediamine is preferably used as the main chemical structure of B. The main chemical structure of B as used herein is a structure that accounts for 50 mol% or more of the entire B. More preferably 60 mol% or more, and still more preferably 80 mol% or more. When the diamine residue derived from p-phenylenediamine is used as the polyamic acid resin having a main chemical structure of B, a polyimide resin film obtained by firing a polyamic acid resin composition containing the polyamic acid resin has a small coefficient of thermal linear expansion, and can be preferably used as a substrate for a flexible device.

It is particularly preferable that a in the general formula (10) has a chemical structure mainly composed of a 4-valent tetracarboxylic acid residue represented by the chemical formula (11) or (12), and B has a chemical structure mainly composed of a 2-valent diamine residue represented by the chemical formula (13).

In addition, in order to improve coatability to a support and resistance to oxygen plasma and UV ozone treatment used for cleaning and the like, B may contain a diamine residue derived from a silicon-containing diamine such as 1, 3-bis (3-aminopropyl) tetramethyldisiloxane or 1, 3-bis (4-anilino) tetramethyldisiloxane. When the diamine residue derived from these silicon-containing diamines is contained, it is preferable that the diamine residue is contained in a range of 1 to 30 mol% of the entire B.

For the polyamic acid (a), the end can be capped with a capping agent. In the synthesis of the polyamic acid, the polyamic acid can be adjusted to a preferred molecular weight by reacting the acid dianhydride and the diamine with the end capping agent.

When the terminal monomer is a diamine, a dicarboxylic anhydride, a monocarboxylic acid chloride, a monocarboxylic acid active ester compound, a dialkyl dicarbonate, or the like can be used as a capping agent in order to cap the amino group.

When the terminal monomer is an acid dianhydride, a monoamine, a monool, or the like can be used as an end-capping agent for capping the acid anhydride group.

The polyamic acid resin composition of the present invention contains a solvent described later, and the concentration of the polyamic acid (a) in the polyamic acid resin composition is preferably 3% by mass or more, and more preferably 5% by mass or more, with respect to 100% by mass of the polyamic acid resin composition. Further, it is preferably 40% by mass or less, and more preferably 30% by mass or less. When the concentration of the resin is 3% by mass or more, the thickness of the polyimide resin film can be easily increased, and when the concentration is 40% by mass or less, (a) the polyamic acid is sufficiently dissolved in the polyamic acid resin composition, and thus a homogeneous polyimide resin film can be easily obtained.

(a) The weight average molecular weight (Mw) of the polyamic acid is preferably 200,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less in terms of polystyrene using Gel Permeation Chromatography (GPC). Within this range, the viscosity of the polyamic acid in the polyamic acid resin composition can be prevented from unnecessarily increasing even if the concentration of the polyamic acid is high, such as 30 mass% or more. The weight average molecular weight is preferably 2,000 or more, more preferably 3,000 or more, and still more preferably 5,000 or more. If the weight average molecular weight is 2,000 or more, the viscosity of the polyamic acid resin composition produced therefrom is not excessively lowered, and the polyamic acid resin composition can have good coatability.

In the general formula (10), r represents the number of repeating units of the structural unit of the resin, and may be in a range satisfying the weight average molecular weight. r is preferably 5 or more, more preferably 10 or more. Further, it is preferably 1000 or less, and more preferably 500 or less.

< (b) the compound represented by the general formula (1)

In the first and second embodiments of the polyamic acid resin composition of the present invention, by including (b) the compound represented by the general formula (1) in the polyamic acid resin composition, adhesion to a support such as glass or an inorganic film such as SiOx can be dramatically improved as compared with the conventional methods, while mechanical properties and visible light transmittance of a polyimide resin film obtained by firing the polyamic acid resin composition are impaired.

When firing described later, X in the general formula (1) reacts with polyamic acid in the polyamic acid resin composition, and Y undergoes a condensation reaction with a polar group on the surface of a support such as glass and a polar group on the surface of an inorganic film such as SiOx, thereby increasing the adhesion of the obtained polyimide resin film to the support such as glass and the inorganic film such as SiOx.

In the general formula (1), X is preferably at least 1 species represented by any one of the general formulae (4) to (7).

[ chemical formula 10]

In the general formulae (4) to (7), R⁴～R⁸Each independently represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atomsA hydrocarbon group, an optionally partially substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an acyl group having 1 to 4 carbon atoms. In the general formulae (4) to (7), R is represented by the general formula (4) to (7) in view of the reaction efficiency between (b) the compound represented by the general formula (1) and (a) the polyamic acid, and the mechanical properties and visible light transmittance of the polyimide resin film obtained therefrom⁴～R⁸Preferably each independently a hydrogen atom or a methyl group.

Specific examples of (b) the compound represented by the general formula (1) include p-hydroxyacetanilide, m-hydroxyacetanilide, o-hydroxyacetanilide, p-methoxyacetanilide, o-methoxyacetanilide, p-ethoxyacetanilide, o-ethoxyacetanilide, 2 '-hydroxy-5' -methylacetanilide, 2 ', 5' -dimethoxyacetanilide, 5 '-acetamido-2' -hydroxyacetophenone, N- [4- (hydroxymethyl) phenyl ] acetamide, N- (4-hydroxyphenyl) methacrylamide, p-acetoacetamide, m-acetoacetamide, o-acetoacetamide, p-ethoxyacetanilide, 2 ', 4' -dimethoxyacetanilide, 2 ', 5' -dimethoxyacetanilide, p-ethoxyacetanilide, p-methoxyacetanilide, p-ethoxyacetanilide, p-methylacetanilide, p-N-2 ', 4' -dimethoxyacetanilide, p-ethoxyacetanilide, p-methylacetanilide, p-b, 4 ' -methoxyformanilide, 4 ' -ethoxy-3-hydroxybutylaniline, 3-hydroxyphenyl urea, (4-methoxyphenyl) urea, (4-ethoxyphenyl) urea, 4 ' -acetoxyacetanilide, (3-hydroxyphenyl) ethyl carbamate, salicylanilide, p-benzacetamide (p-benzanidide), 3 ' -amino-4 ' -methoxyacetanilide, 3-amino-4-methoxybenzanilide, 4-acetamidothiophenol (4-acetamidothiophenol), 3 ' - (methylthio) acetanilide, 3-Hydroxy-2-naphthylaniline (3-Hydroxy-2-naphthylaniline), 3-Hydroxy-2 ' -methyl-2-naphthylaniline, 3-hydroxy-N- (1-naphthyl) -2-naphthamide, 3-hydroxy-N- (2-naphthyl) -2-naphthamide (3-hydroxy-N- (1-naphthyl) -2-naphthamide), 3-hydroxy-2 ', 4 ' -dimethyl-2-naphthylaniline, 3-hydroxy-2 ' -methoxy-2-naphthylaniline, and the like. These 1 or 2 or more kinds can be used in combination.

Further, as specific examples of the compound (b) represented by the general formula (1), the following monoamine compounds can be used as they are or with an amino group protected. The amino group is protected to suppress oxidation at the time of firing described later, and the visible light transmittance of the obtained polyimide resin film is higher than that of the polyimide resin film without protecting the amino group. The method for protecting an amino group can use a known method, and in particular, a method of reacting it with a dialkyl dicarbonate is preferable. Examples of the monoamine compound include 4-aminophenol, 3-aminophenol, 2-aminophenol, 4-amino-m-cresol, 4-amino-o-cresol, 4-amino-2-methoxyphenol, 3-amino-4-methoxyphenol, 4-amino-3, 5-xylenol, 5-amino-1-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, 6-amino-1-naphthol, 3-amino-2-naphthol, 3, 4-dimethoxyaniline, 3, 5-dimethoxyaniline, 2, 3-dimethoxyaniline, 2, 4-dimethoxyaniline, 2, 5-dimethoxyaniline, 2, 6-dimethoxyaniline, 3,4, 5-trimethoxyaniline, etc. These 1 or 2 or more kinds can be used in combination.

In the general formula (1), Y is preferably at least 1 selected from a hydroxyl group, an alkoxy group and an acetoxy group, and more preferably a hydroxyl group or an acetoxy group, from the viewpoints of (b) the reaction efficiency between the compound represented by the general formula (1) and the polar group on the surface of the support such as glass and the polar group on the surface of the inorganic film such as SiOx, and the visible light transmittance of the obtained polyimide resin film.

Among them, the compound represented by the general formula (1) is particularly preferably a compound represented by the general formula (8) or (9).

[ chemical formula 11]

In the general formula (8) or (9), R⁹And R¹⁰Is a hydrocarbon group having 1 to 3 carbon atoms, and p and q are 0 or 1.

Specific examples of the compound represented by the general formula (8) or (9) (b) include p-hydroxyacetanilide, m-hydroxyacetanilide, o-hydroxyacetanilide, 2 ' -hydroxy-5 ' -methylacetanilide, and 4 ' -acetoxyacetanilide.

Further, if the group containing a nitrogen atom (corresponding to X) is separated from the substitution position of the group containing a hydroxyl group or an ester structure (corresponding to Y), the respective reaction efficiencies of X and polyamic acid and Y and the polar group on the surface of a support such as glass and the polar group on the surface of an inorganic film such as SiOx become higher than those in the case where the substitution position is close to each other, and therefore, it is preferable. From such a viewpoint, it is particularly preferable to use p-hydroxyacetanilide, m-hydroxyacetanilide, or 4' -acetoxyacetanilide as the compound (b) represented by the general formula (8) or (9).

In the first and second embodiments of the polyamic acid resin composition of the present invention, the content of the compound represented by the general formula (1) of (b) is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of (a) polyamic acid. When the content is 0.05 parts by mass or more, a material having high adhesion to a support such as glass or an inorganic film such as SiOx can be obtained as compared with a case where the content is less than 0.05 parts by mass. The content is preferably 5.0 parts by mass or less, and more preferably 3.0 parts by mass or less. When the content is 5.0 parts by mass or less, the polyimide resin film after firing has higher mechanical properties and higher visible light transmittance than when the content exceeds 5.0 parts by mass.

The content of the compound represented by the general formula (1) (b) in the polyamic acid resin composition can be determined by a liquid chromatography-mass spectrometry (LC-MS) method,¹H-NMR method was used for the quantification. From the obtained content (% by mass) and the content of other components, the content ratio of the compound represented by the general formula (1) (b) to the polyamic acid (a) in the polyamic acid resin composition can be determined. For example, in the LC-MS method, the content of the compound represented by the general formula (1) (b) in the polyamic acid resin composition can be determined by diluting the polyamic acid resin composition with N, N-dimethylformamide and directly performing LC-MS analysis. The content of the compound represented by the general formula (1) (b) in the polyamic acid resin composition detected by the LC-MS method is preferably 0.001 mass% or more, and more preferably 0.003 mass% or more. Further, it is preferably 2.0% by mass or less, and more preferably 1.2% by mass or less. Within this range, the ratio of the compound represented by the general formula (1) (b) relative to the polyamic acid (a) variesIs a preferred range.

< solvent >

The polyamic acid resin composition of the invention comprises a solvent. A coating film containing polyamic acid can be formed by applying such a polyamic acid resin composition as described below to various supports. The obtained coating film is heated and baked to imidize the coating film, whereby a polyimide resin film which can be used as a substrate for an electronic device can be produced.

The solvent is not particularly limited, and a known solvent can be used. The following substances can be used alone or in combination of 2 or more, for example: n-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, γ -butyrolactone, ethyl lactate, 1, 3-dimethyl-2-imidazolidinone, N' -dimethylpropyleneurea, 1,3, 3-tetramethylurea, dimethyl sulfoxide, sulfolane, propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, water, a solvent described in international publication No. 2017/099183, and the like.

The preferable content of the solvent in the polyamic acid resin composition is not particularly limited, and is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, preferably 2000 parts by mass or less, and more preferably 1500 parts by mass or less, with respect to 100 parts by mass of the polyamic acid (a). If the viscosity is within the range satisfying such a condition, the viscosity can be adjusted to be suitable for coating, and the film thickness after coating can be easily adjusted.

The viscosity of the polyamic acid resin composition of the present invention is preferably 20 to 10,000 mPas, and more preferably 50 to 8,000 mPas. A polyimide resin film having a sufficient film thickness can be obtained by setting the viscosity to 20mPa · s or more, and good coatability can be ensured by setting the viscosity to 10,000mPa · s or less.

[ first mode ]

The first embodiment of the polyamic acid resin composition of the present invention is a polyamic acid resin composition comprising (a) a polyamic acid and (b) a compound represented by the general formula (1), wherein the polyamic acid (a) is a polyamic acid having a repeating unit represented by the general formula (10), and the polyamic acid resin composition is a non-photosensitive resin composition.

[ chemical formula 12]

In the general formula (10), A represents a 4-valent tetracarboxylic acid residue having 2 or more carbon atoms, and has a chemical structure mainly composed of a 4-valent tetracarboxylic acid residue represented by the chemical formula (11) or (12). B represents a 2-valent diamine residue having 2 or more carbon atoms, and has a chemical structure mainly composed of the 2-valent diamine residue represented by chemical formula (13). R¹¹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion. r is a positive integer.

As described above, r is preferably 5 or more, and more preferably 10 or more. The upper limit of r is not particularly limited, and is usually 1000 or less. When r is 2 or more, a plurality of a in the general formula (10) may be the same or different, and similarly, b may be the same or different.

[ chemical formula 13]

In the general formula (10), a has a chemical structure mainly composed of a 4-valent tetracarboxylic acid residue represented by the chemical formula (11) or (12), and B has a chemical structure mainly composed of a 2-valent diamine residue represented by the chemical formula (13), and thus the polyimide resin film obtained by firing has a small thermal linear expansion coefficient and high mechanical strength, and therefore can be preferably used as a flexible device substrate.

On the other hand, photosensitive components such as photoacid generators represented by quinone diazide compounds are not preferably contained when used as flexible device substrates because they have low heat resistance and are rapidly decomposed when heated at 350 ℃ or higher, and the polyimide resin film obtained by firing becomes brittle. The term "not containing" as used herein means a content which does not substantially exhibit photosensitivity. The content is preferably less than 1.0 part by mass, more preferably less than 0.5 part by mass, and still more preferably less than 0.1 part by mass, relative to 100 parts by mass of (a) polyamic acid. By setting the content of the photosensitive component to less than 1.0 part by mass, the embrittlement of the polyimide resin film at the time of firing can be suppressed, and a film having mechanical properties and visible light transmittance required for a flexible device substrate can be obtained. When the content is less than 1.0 part by mass, the resin composition exhibits substantially no photosensitivity and is non-photosensitive.

[ second mode ]

The second embodiment of the polyamic acid resin composition of the present invention is a polyamic acid resin composition comprising (a) a polyamic acid and (b) a compound represented by the general formula (1), wherein a polyimide resin film obtained by coating the polyamic acid resin composition on a support and then baking the coated polyamic acid resin composition at 500 ℃ for 30 minutes in an inert gas atmosphere has an elongation at break of 5 to 150% when the film thickness is 10 μm.

The polyamic acid resin composition according to the second embodiment of the present invention is preferably a non-photosensitive resin composition in view of the elongation at break of the polyimide resin film. As described above, the non-photosensitive resin composition means that the content of the photosensitive component is a content which does not substantially exhibit photosensitivity.

< elongation at break of polyimide resin film >

In the polyamic acid resin composition according to the first aspect of the present invention, a polyimide resin film obtained by applying the polyamic acid resin composition to a support and then firing the composition at 500 ℃ for 30 minutes in an inert gas atmosphere preferably has an elongation at break of 5 to 150% when the film thickness is 10 μm. In the polyamic acid resin compositions according to the first and second embodiments of the present invention, the elongation at break is more preferably 10% or more, and still more preferably 15% or more. Further, it is preferably 100% or less, and more preferably 60% or less. When the elongation at break is in this range, the polyimide resin film is less likely to be broken during or after a peeling step from a support, which will be described later, and thus the polyimide resin film can be used as a substrate for a flexible device. The elongation at break is defined as a value measured by a method for producing a polyimide film and a method for measuring mechanical properties in examples described later.

< inorganic particles >

The polyamic acid resin composition of the present invention may contain inorganic particles for the purpose of further improving heat resistance. Examples of the inorganic particles used for such a purpose include metal inorganic particles such as platinum, gold, palladium, silver, copper, nickel, zinc, aluminum, iron, cobalt, rhodium, ruthenium, tin, lead, bismuth, and tungsten, and metal oxide inorganic particles such as silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, calcium carbonate, and barium sulfate.

The shape of the inorganic particles is not particularly limited, and examples thereof include spherical, elliptical, flat, rod-like, and fibrous. In order to suppress an increase in the surface roughness of the polyimide resin film containing inorganic particles, the average particle diameter of the inorganic particles is preferably 1nm or more and 100nm or less, more preferably 1nm or more and 50nm or less, and still more preferably 1nm or more and 30nm or less.

The content of the inorganic particles in the polyamic acid resin composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 50 parts by mass or less, with respect to 100 parts by mass of the polyamic acid (a). When the content of the inorganic particles is 3 parts by mass or more, the heat resistance is remarkably higher than that in the case of the content not satisfying the condition, and when the content is 100 parts by mass or less, the degree of deterioration of toughness of the polyimide resin film obtained by firing is smaller than that in the case of the content exceeding the condition.

< surfactant >

The polyamic acid resin composition of the present invention preferably contains a surfactant in order to further improve coatability to a support. Examples of the surfactant include fluorine-based surfactants such as "Fluorad" (registered trademark) manufactured by sumitomo 3M corporation, "MEGAFAC" (registered trademark) manufactured by DIC corporation, and "Surufuron" (registered trademark) manufactured by asahi nitre corporation; organosiloxane surfactants such as "POLYFLOW" (registered trademark), "Granol" (registered trademark), and BYK manufactured by BYK-Chemie GmbH, manufactured by shin-Etsu chemical Co., Ltd., "DBE manufactured by Ltd.,; and a propylene polymer surfactant such as POLYFLOW manufactured by Kyowa Kagaku K.K. The content of the surfactant in the polyamic acid resin composition is preferably 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyamic acid (a).

The polyamic acid resin composition of the present invention may contain a thermal crosslinking agent, a thermal acid generator, a leveling agent, a viscosity modifier, an antioxidant, an inorganic pigment, an organic pigment, a dye, and the like, within a range not to impair the effects of the present invention.

< method for polymerizing polyamic acid >

The polyamic acid can be polymerized by a known method. For example, a polyamic acid can be obtained by polymerizing tetracarboxylic acid, a corresponding acid dianhydride, an active ester, an active amide, or the like as an acid component, and diamine, a corresponding trimethylsilylated diamine, or the like as a diamine component in a reaction solvent. The polyamic acid may be a salt of a carboxyl group with an alkali metal ion, an ammonium ion, or an imidazolium ion, or may be an ester of a carboxyl group with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms.

The reaction solvent to be supplied to the polymerization of the polyamic acid is not particularly limited, and a known one can be used. The following substances can be used alone or in combination of 2 or more, for example: n-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, γ -butyrolactone, ethyl lactate, 1, 3-dimethyl-2-imidazolidinone, N' -dimethylpropyleneurea, 1,3, 3-tetramethylurea, dimethyl sulfoxide, sulfolane, propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, water, a reaction solvent described in international publication No. 2017/099183, and the like.

The reaction temperature is preferably-20 ℃ to 150 ℃, and more preferably 0 ℃ to 100 ℃. The reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours. The number of moles of the diamine used in the reaction is preferably equal to the number of moles of the tetracarboxylic acid. When the amount is equal, a polyimide resin film having high mechanical properties can be easily obtained from the polyamic acid resin composition.

The obtained polyamic acid solution can be used as it is as the polyamic acid resin composition of the present invention. In this case, the same solvent as that used in the preparation of the polyamic acid resin composition is used as the reaction solvent, or the solvent is added after the completion of the reaction, whereby the target polyamic acid resin composition can be obtained without isolating the polyamic acid (a).

In addition, a part or all of the repeating units of the obtained polyamic acid may be imidized by a known method, or may be esterified. In this case, the polyamic acid solution obtained by polymerizing the polyamic acid may be used as it is for the next reaction, or may be used after the polyamic acid is separated for the next reaction.

< method for producing Polyamic acid resin composition >

The polyamic acid (a), the compound represented by the general formula (1), and if necessary, inorganic particles, a surfactant, and the like are dissolved in a solvent, whereby the polyamic acid resin composition of the present invention can be obtained. Examples of the dissolving method include stirring and heating. The heating temperature is usually from room temperature to 80 ℃. The order of dissolving the components is not particularly limited, and for example, there is a method of dissolving compounds having low solubility in order. In addition, by dissolving other components in a component that is likely to generate bubbles when the surfactant or the like is dissolved with stirring and then adding the component at the end, it is possible to prevent the other components from being dissolved poorly due to the generation of bubbles.

The polyamic acid resin composition obtained by the above-mentioned production method is preferably filtered with a filter to remove foreign matters such as dirt.

< method for producing polyimide resin film >

The polyamic acid resin composition of the present invention can be heated and baked to be imidized to obtain a polyimide resin film.

The method for producing a polyimide resin film of the present invention includes, for example, a step of applying the above polyamic acid resin composition to a support and a step of heating and baking the applied film to imidize the film.

First, the polyamic acid resin composition of the present invention is coated on a support. Examples of the support include a wafer substrate such as silicon and gallium arsenide; glass substrates such as sapphire glass, soda-lime glass, alkali-free glass and the like; metal substrates or metal foils such as stainless steel and copper; a ceramic substrate, and the like. Among them, alkali-free glasses are preferable from the viewpoint of surface smoothness and dimensional stability during heating.

Examples of the method for applying the polyamic acid resin composition include spin coating, slit coating, dip coating, spray coating, and printing, and these may be combined. When the polyimide resin film is used as a substrate for an electronic device, it is necessary to coat the polyimide resin film on a large-sized support, and therefore the slit coating method is particularly preferably used.

After coating, the coating film of the polyamic acid resin composition is usually dried. As a drying method, drying under reduced pressure, drying by heating, or a combination of these can be used. As a method of drying under reduced pressure, for example, a support having a coating film formed thereon is placed in a vacuum chamber, and the pressure in the vacuum chamber can be reduced. In addition, a hot plate, an oven, infrared rays, or the like can be used for the heat drying.

Finally, the polyimide resin film can be produced by heating and baking the film at a temperature in the range of 180 ℃ to 600 ℃ to imidize the coating film.

The polyimide resin film obtained through the above steps is generally used in the next step without being peeled off when used as a substrate of an electronic device. However, the polyimide resin film peeled from the support by a peeling method described later may be used to proceed to the next step. When the support is used in the next step without peeling, the pressure generated is preferably less than 25MPa in order to prevent the decrease in the step passability due to the warp of the support. The pressure is generally measured using a film stress measuring device. The warp amount of the substrate on which the polyimide resin film was formed was measured, and the structure thereof was calculated. In order to exclude the influence of moisture absorption of the polyimide resin film, it is preferable to perform the measurement in a dried state.

The polyimide resin film of the present invention is preferably used as a substrate for an electronic device. Examples of the electronic device include display devices such as an organic EL display, a liquid crystal display, a micro LED display, electronic paper, and a color filter; light receiving devices such as scintillators and solar cells; sensor components such as touch panels, and the like.

The thickness of the polyimide resin film of the present invention is not particularly limited, but is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more. The film thickness is preferably 100 μm or less, more preferably 70 μm or less, and still more preferably 50 μm or less. When the film thickness is 3 μm or more, sufficient mechanical properties can be obtained as a substrate for an electronic device. When the film thickness is 50 μm or less, sufficient toughness can be obtained as a substrate for an electronic device.

The polyimide resin film of the present invention has a visible light transmittance of preferably 60% or more, more preferably 65% or more, and even more preferably 70% or more at a wavelength of 500 nm. By setting the visible light transmittance to 60% or more, when the polyimide resin film is used as a substrate of a light receiving device, light absorption by the polyimide resin film can be suppressed, and good light receiving sensitivity can be maintained.

< laminate >

The laminate of the present invention has an inorganic film on the polyimide resin film. Examples of the inorganic film include silicon oxide (SiOx), silicon nitride (SiNy), and silicon oxynitride (SiOxNy), and these can be used as a single layer or as a stack of a plurality of layers. These inorganic films may be alternately laminated with an organic film such as polyvinyl alcohol, for example. The method for forming these inorganic films is preferably performed by vapor deposition such as Chemical Vapor Deposition (CVD) or Physical Vapor Deposition (PVD).

The laminate of the present invention may further include a polyimide resin film on the inorganic film. In addition, further, an inorganic film may also be provided thereon.

The polyimide resin film formed on the support can be used as a laminate as described above.

As described below, the laminate as described above can be used as a substrate of an electronic device.

< method for manufacturing electronic device >

The method for manufacturing an electronic device of the present invention includes the steps of: a step of forming the polyimide resin film on a support; forming a display device, a light receiving device, or a sensor member on the polyimide resin film; and a step of peeling the polyimide resin film from the support.

First, a polyimide resin film is produced on a support such as a glass substrate according to the above-described method. In this case, an undercoat layer may be provided on the support in advance in order to facilitate peeling from the support described later. Examples thereof include: the support is coated with a release agent or provided with a sacrificial layer. Examples of the release agent include silicone-based, fluorine-based, aromatic polymer-based, and alkoxysilane-based. Examples of the sacrificial layer include a metal film, a metal oxide film, and an amorphous silicon film.

An inorganic film is provided on the polyimide resin film as needed. This can prevent moisture and oxygen from permeating the polyimide resin film from the outside of the substrate and causing deterioration of the pixel drive element and the light-emitting element over time. Examples of the inorganic film include those described above.

If necessary, a polyimide resin film is formed on the inorganic film, or an inorganic film is further formed, whereby a substrate for an electronic device including a plurality of inorganic films and polyimide resin films can be manufactured. The polyamic acid resin compositions used for producing the polyimide resin films are preferably the same polyamic acid resin composition from the viewpoint of process simplification.

Next, the constituent elements of the display device, the light receiving device, or the sensor member are formed on the obtained polyimide resin film (on the inorganic film, if present). For example, in the case of an organic EL display, a TFT as an image driving element, a first electrode, an organic EL light emitting element, a second electrode, and a sealing film are formed in this order to form an image display element. In the case of a color filter substrate, a black matrix is formed as necessary, and then colored pixels such as red, green, and blue are formed. In the case of a substrate for a touch panel, a wiring layer and an insulating layer are formed.

Finally, the support and the polyimide resin film are peeled off from each other at the interface therebetween, and the support is removed. Examples of the method of peeling include a so-called laser peeling method in which the support and the polyimide resin film are peeled from each other at the interface therebetween by irradiation with a laser beam, a mechanical peeling method, and a method in which the support is etched. In the case of laser lift-off, a support such as a glass substrate is irradiated with laser light from the side opposite to the side on which the polyimide resin film and the element are formed. This enables the element to be peeled without being damaged.

As the laser light, a laser light having a wavelength ranging from ultraviolet light to infrared light can be used, but ultraviolet light is particularly preferable. More preferably, it is 308nm excimer laser. The peeling energy is preferably 250mJ/cm²Hereinafter, more preferably 200mJ/cm²The following.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

< evaluation method >

[1] Production of glass substrate with polyimide resin film

The polyamic acid resin composition was spin-coated on an 8-inch glass substrate using a spin coater (1H-DX 2 manufactured by Mikasa Corporation). Then, it was dried at 110 ℃ for 10 minutes using a hot plate (HPD-3000 BZN manufactured by AS ONE Corporation). Then, a polyimide resin film having a film thickness of 10 μm was formed on a glass substrate by heating the glass substrate from 50 ℃ in a nitrogen atmosphere (oxygen concentration: 20ppm or less) for 30 minutes at 220 ℃ and then for 30 minutes at 500 ℃ using an inert oven (Koyo Thermo Systems Co., Ltd., INH-21CD manufactured by Ltd.). The temperature increase rate was set to 4 ℃/min. Hereinafter, the substrate is referred to as a glass substrate with a polyimide resin film.

[2] Production of CVD substrate having polyimide resin film

On an 8-inch glass substrate, the substrate was formed of SiO by CVD₂Layer and Si₃N₄The gas barrier film formed by laminating layers is made of SiO₂The layer is formed as the uppermost layer. Then, with the above [1]]The same procedure as in (1) was repeated to form a polyimide resin film having a thickness of 10 μm on the laminated film. This is hereinafter referred to as a CVD substrate with a polyimide resin film.

[3] Evaluation of adhesion

The polyimide resin films of the polyimide resin film-attached glass substrate and the polyimide resin film-attached CVD substrate obtained by the methods described in [1] and [2] above were cut into strips having a width of 10mm, and then the ends were peeled off from the substrates to obtain measurement samples. The 90 ℃ peel strength was measured using a small bench-top tester (manufactured by Nidec-Shimpo Corporation, Stand FGS-50V-H, digital tensile tester FGJN-5). The width of the test piece was 10mm, the test speed was 50 mm/min, and the average value of 8 positions except for the uppermost and lowermost values was calculated, assuming that the number of measurements n was 10. The 90 DEG peel strength was classified into 4 grades A to D, and when the glass substrate and the CVD substrate were both C or more, the adhesion was judged to be good, and when either or both of the glass substrate and the CVD substrate was D, the adhesion was judged to be poor.

A: a 90 DEG peel strength of 0.8N/cm or more

B: the 90-degree peel strength is more than 0.4N/cm and less than 0.8N/cm

C: the 90-degree peel strength is more than 0.2N/cm and less than 0.4N/cm

D: the 90 DEG peel strength is less than 0.2N/cm.

[4] Evaluation of mechanical Properties (elongation at Break, tensile stress at maximum, Young's modulus)

The polyimide resin film of the glass substrate with the polyimide resin film obtained by the method described in [1] above was cut into a strip shape having a width of 10mm and a length of 80mm, and then peeled from the glass substrate to obtain a measurement sample. The elongation at break from the original length was measured using a Tensilon Universal Material tester (Orientec Co., Ltd., RTM-100 manufactured by Ltd.) according to Japanese Industrial standards (JIS K7127: 1999). The width of the test piece was 10mm, the chuck interval was 50mm, the test speed was 50 mm/min, and the average value of the test piece and the chuck interval was 10.

[5] Evaluation of visible light transmittance

The glass substrate with a polyimide resin film obtained by the method described in [1] above was measured for transmittance at a wavelength of 500nm using an ultraviolet-visible spectrophotometer (MultiSpec-1500, manufactured by Shimadzu corporation).

< manufacturing example >

The compounds used in the production examples are shown below.

(polymerization raw Material)

BPDA: 3,3 ', 4, 4' -Biphenyltetracarboxylic dianhydride

And (3) PMDA: pyromellitic dianhydride

p-PDA: p-phenylenediamine

And (3) DAE: 4, 4' -diaminodiphenyl ether

4, 4' -DDS: 4, 4' -diaminodiphenyl sulfone

DIBOC: di-tert-butyl dicarbonate

NMP: n-methyl-2-pyrrolidone.

(additives)

Compound b-1: p-hydroxyacetanilide

[ chemical formula 14]

Compound b-2: m-hydroxyacetanilide

[ chemical formula 15]

Compound b-3: p-methoxy acetanilide

[ chemical formula 16]

Compound b-4: 4' -acetoxyacetanilide

[ chemical formula 17]

Compound b-5: 3-hydroxyphenyl ureas

[ chemical formula 18]

Compound b-6: KBE-585 (50% methanol solution of 3-ureidopropyltriethoxysilane, manufactured by shin-Etsu chemical Co., Ltd.)

[ chemical formula 19]

Compound b-7: KBE-903 (3-aminopropyltriethoxysilane, manufactured by shin-Etsu chemical Co., Ltd.)

[ chemical formula 20]

Compound b-8: KBE-903 adduct of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride

[ chemical formula 21]

Compound b-9: decanoyl chloride adduct of 2-amino aminophenol

[ chemical formula 22]

Quinone diazide compound c-1: naphthoquinone diazide-5-sulfonyl chloride adduct of TrisP-PA (manufactured by chemical industries, Ltd., Japan)

[ chemical formula 23]

Surfactant A: BYK-333(BYK Chemie Japan K.k. manufactured)

Surfactant B: POLYFLOW No.77 (available from Kyoeisha chemical Co., Ltd.).

Production example 1: polyamic acid resin solution a-1

A300 mL four-necked flask was equipped with a thermometer and a stirring rod with a stirring blade. Next, NMP90g was put into the nitrogen stream, and the temperature was raised to 60 ℃. After the temperature was raised, 5.41g (50mmol) of p-PDA was poured in with stirring, and the mixture was washed with 10g of NMP. After confirming the dissolution of p-PDA, 14.71g (50mmol) of BPDA was charged and washed with 10g of NMP. After 4 hours of reaction at 60 ℃, the reaction mixture was cooled to obtain a polyamic acid resin solution (a-1) having a solid content concentration of 15.5 mass%.

Production example 2: polyamic acid resin solution a-2

A300 mL four-necked flask was equipped with a thermometer and a stirring rod with a stirring blade. Then, 80g of NMP was charged under a stream of dry nitrogen, and the temperature was raised to 60 ℃. After the temperature was raised, 5.41g (50mmol) of p-PDA was poured in with stirring, and the mixture was washed with 10g of NMP. After confirming the dissolution of p-PDA, 7.63g (35mmol) of PMDA and 4.41g (15mmol) of BPDA were charged, and the mixture was washed with 10g of NMP. After 4 hours of reaction at 60 ℃, the reaction mixture was cooled to obtain a polyamic acid resin solution (a-2) having a solid content concentration of 14.9 mass%.

Production example 3: polyamic acid resin solution a-3

A300 mL four-necked flask was equipped with a thermometer and a stirring rod with a stirring blade. Then, 80g of NMP was charged under a stream of dry nitrogen, and the temperature was raised to 60 ℃. After the temperature was raised, 5.41g (50mmol) of p-PDA was poured in with stirring, and the mixture was washed with 10g of NMP. Dissolution of p-PDA was confirmed, and 0.44g (1mmol) of DIBOC diluted with 5g of NMP was added dropwise over 30 minutes, followed by washing with 5g of NMP. 14.71g (50mmol) of BPDA was further charged, and the mixture was washed with 10g of NMP. After 4 hours of reaction at 60 ℃, the reaction mixture was cooled to obtain a polyamic acid resin solution (a-3) having a solid content concentration of 15.7 mass%.

Production example 4: polyamic acid resin solution a-4

A300 mL four-necked flask was equipped with a thermometer and a stirring rod with a stirring blade. Then, 80g of NMP was charged under a stream of dry nitrogen, and the temperature was raised to 60 ℃. After the temperature was raised, 4.33g (40mmol) of p-PDA and 2.00g (10mmol) of DAE were put in while stirring, and washed with 10g of NMP. Dissolution of p-PDA and DAE was confirmed, and 0.44g (1mmol) of DIBOC diluted with 5g of NMP was added dropwise over 30 minutes, followed by washing with 5g of NMP. 14.71g (50mmol) of BPDA was further charged, and the mixture was washed with 10g of NMP. After 4 hours of reaction at 60 ℃, the reaction mixture was cooled to obtain a polyamic acid resin solution (a-4) having a solid content concentration of 16.3 mass%.

Production example 5: polyamic acid resin solution a-5

A300 mL four-necked flask was equipped with a thermometer and a stirring rod with a stirring blade. Then, 90g of NMP was charged under a dry nitrogen stream, and the temperature was raised to 60 ℃. After the temperature was raised, 4.33g (40mmol) of p-PDA and 2.48g (10mmol) of 4, 4' -DDS were put in while stirring, and then washed with 10g of NMP. After confirming that p-PDA and 4, 4' -DDS were dissolved, BPDA14.71g (50mmol) was charged, and the mixture was washed with NMP10 g. After 4 hours of reaction at 60 ℃, the reaction mixture was cooled to obtain a polyamic acid resin solution (a-5) having a solid content concentration of 16.4 mass%.

Production example 6: polyamic acid resin compositions P-1 to P-22

The additive was added to the polyamic acid resin solution obtained in production examples 1 to 5 so that the amount of the active ingredient added was as shown in tables 1 to 2, and the mixture was stirred for 1 hour. The resulting solution was filtered through a polyethylene filter (filter pore size: 0.2 μm). The polyamic acid resin solution was directly filtered with a polyethylene filter (filter pore size 0.2 μm) without adding an additive. Thus, polyamic acid resin compositions P-1 to P-22 were obtained. However, no additive was added to P-15.

Examples 1 to 16 and comparative examples 1 to 6

Using the polyamic acid resin compositions P-1 to P-22 obtained in production example 6, polyimide resin films were produced on glass substrates and CVD substrates in accordance with the above-described methods. The obtained polyimide resin was evaluated for adhesion, mechanical properties, and visible light transmittance by the methods described above. However, with respect to the polyamic acid resin composition P-20 of comparative example 6, since the film after firing became brittle and a self-supporting film could not be obtained, evaluation of only the visible light transmittance was performed

The evaluation results of the compositions, adhesion, mechanical properties and visible light transmittance of examples 1 to 16 and comparative examples 1 to 6 are shown in tables 1 and 2.

[ Table 1]

[ Table 2]

Example 101

On the polyimide resin film obtained in example 1, a film was formed of SiO by CVD₂Layer and Si₃N₄The gas barrier film formed by laminating the layers is formed. Next, a polyimide resin film was formed on the laminated film in the same manner as in example 1, and a gas barrier film was further formed on the polyimide resin film in the same manner as described above. Then, a TFT is formed on the gas barrier film toForming a state covering the TFT to contain Si₃N₄The insulating film of (2). Next, after forming a contact hole in the insulating film, a wiring connected to the TFT is formed through the contact hole.

Further, in order to planarize irregularities caused by the formation of the wiring, a planarization film is formed. Next, on the obtained planarization film, a first electrode formed of ITO was formed so as to be connected to a wiring. Then, a resist is applied, prebaked, exposed through a mask having a desired pattern, and developed. The resist pattern was used as a mask, and patterning was performed by wet etching using an ITO etchant. Then, the resist pattern was peeled off using a resist peeling liquid (a mixed liquid of monoethanolamine and diethylene glycol monobutyl ether). The peeled substrate was washed with water and dehydrated by heating to obtain an electrode substrate with a planarizing film. Next, an insulating film having a shape covering the periphery of the first electrode is formed.

Further, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a mask having a desired pattern. Then, a second electrode formed of Al/Mg is formed over the entire surface over the substrate. Further, forming the silicon containing layer by CVD₂Layer and Si₃N₄A laminated sealing film of layers. Finally, the glass substrate was irradiated with a laser beam (wavelength: 308nm) from the side where the polyimide resin film was not formed, and peeled off at the interface with the polyimide resin film. The irradiation energy at this time was set to 200mJ/cm²。

In this manner, an organic EL display device formed on a polyimide resin film was obtained. When a voltage is applied through the driving circuit, good light emission is exhibited.

Example 201

Paracetanilide was diluted with methanol in this order to prepare a standard curve solution, and LC-MS measurement was performed by electrospray ionization (ESI) to prepare a standard curve. Then, N-dimethylformamide was added to polyamic acid resin composition P-1(208.73mg) obtained in production example 6 to give a total volume of 2mL, and LC-MS measurement was carried out in the same manner, whereby the concentration of P-hydroxyacetanilide was 0.077% by mass.

Claims

1. A polyamic acid resin composition comprising (a) a polyamic acid and (b) a compound represented by the general formula (1), (a) the polyamic acid being a polyamic acid having a repeating unit represented by the general formula (10), the polyamic acid resin composition being a non-photosensitive resin composition,

[ chemical formula 1]

In the general formula (10), A represents a 4-valent tetracarboxylic acid residue having 2 or more carbon atoms, and has a chemical structure mainly composed of a 4-valent tetracarboxylic acid residue represented by the chemical formula (11) or (12); b represents a 2-valent diamine residue having 2 or more carbon atoms and has a chemical structure mainly composed of the 2-valent diamine residue represented by the chemical formula (13); r¹¹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion; r is a positive integer, and r is a positive integer,

[ chemical formula 2]

[ chemical formula 3]

In the general formula (1), R¹Represents a hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 1 to 4 carbon atoms; x represents an organic group containing a nitrogen atom; y represents a group represented by the general formula (2) or (3); l is an integer of 0 to 2, when l is 2, a plurality of R¹May be the same or different; n is 0 or 1; when k is 1 or 2 and k is 2, plural X's may be the same or differentTo be different; m is an integer of 1 to 3, and when m is 2 or more, plural Y's may be the same or different,

[ chemical formula 4]

In the general formulae (2) and (3), σ represents an oxygen atom or a sulfur atom; r²And R³Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; h and j are each 0 or 1.

2. A polyamic acid resin composition comprising (a) a polyamic acid and (b) a compound represented by the general formula (1), wherein a polyimide resin film obtained by applying the polyamic acid resin composition to a support and then firing the composition at 500 ℃ for 30 minutes in an inert gas atmosphere shows an elongation at break of 5 to 150% at a film thickness of 10 [ mu ] m,

[ chemical formula 5]

In the general formula (1), R¹Represents a hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 1 to 4 carbon atoms; x represents an organic group containing a nitrogen atom; y represents a group represented by the general formula (2) or (3); l is an integer of 0 to 2, when l is 2, a plurality of R¹May be the same or different; n is 0 or 1; k is 1 or 2, and when k is 2, a plurality of xs may be the same or different; m is an integer of 1 to 3, and when m is 2 or more, plural Y's may be the same or different,

[ chemical formula 6]

In the general formulae (2) and (3), σ represents an oxygen atom or a sulfur atom, R²And R³Each of which isIndependently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; h and j are each 0 or 1.

3. The polyamic acid resin composition according to claim 2, wherein the polyamic acid resin composition is a non-photosensitive resin composition.

4. The polyamic acid resin composition according to claim 2 or 3, wherein the polyamic acid has a repeating unit represented by the general formula (10),

[ chemical formula 7]

In the general formula (10), A represents a 4-valent tetracarboxylic acid residue having 2 or more carbon atoms, and B represents a 2-valent diamine residue having 2 or more carbon atoms; r¹¹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion; r is a positive integer.

5. The polyamic acid resin composition according to claim 4, wherein in the general formula (10), A has a chemical structure mainly comprising a 4-valent tetracarboxylic acid residue represented by the formula (11) or (12), B has a chemical structure mainly comprising a 2-valent diamine residue represented by the formula (13),

[ chemical formula 8]

6. The polyamic acid resin composition according to any one of claims 1 to 3, wherein Y in the general formula (1) is at least one group selected from the group consisting of a hydroxyl group, an alkoxy group and an acetoxy group.

7. The polyamic acid resin composition according to any one of claims 1 to 3, wherein in the general formula (1), X is at least one group represented by any one of general formulae (4) to (7),

[ chemical formula 9]

In the general formulae (4) to (7), R⁴～R⁸Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be partially substituted, a hydroxyalkyl group having 1 to 6 carbon atoms or an acyl group having 1 to 4 carbon atoms.

8. The polyamic acid resin composition according to claim 7, wherein R in the general formulae (4) to (7)⁴～R⁸Each independently is a hydrogen atom or a methyl group.

9. The polyamic acid resin composition according to any one of claims 1 to 3, wherein the compound (b) represented by the general formula (1) is a compound represented by the following general formula (8) or (9),

[ chemical formula 10]

In the general formulae (8) and (9), R⁹And R¹⁰Is a hydrocarbon group having 1 to 3 carbon atoms, and p and q are 0 or 1.

10. The polyamic acid resin composition according to any one of claims 1 to 3, wherein the content of the compound represented by the general formula (1) (b) is 0.05 part by mass or more and 5.0 parts by mass or less based on 100 parts by mass of the polyamic acid (a).

11. The polyamic acid resin composition according to any one of claims 1 to 3, wherein the content of the compound represented by the general formula (1) (b) in the polyamic acid resin composition, which is detected by LC-MS method, is 0.001 mass% or more and 2.0 mass% or less.

12. A polyimide resin film obtained by imidizing the polyamic acid resin composition according to any one of claims 1 to 11 by heating and firing.

13. A method for producing a polyimide resin film, comprising the steps of: imidizing the polyamic acid resin composition according to any one of claims 1 to 11 by heating and firing.

14. A laminate comprising the polyimide resin film according to claim 12, an inorganic film, and the polyimide resin film according to claim 12, which are laminated in this order.

15. An electronic device comprising the polyimide resin film according to claim 12 as a substrate.

16. The electronic device according to claim 15, wherein the electronic device is a display device, a light receiving device, or a sensor part.

17. A method for manufacturing an electronic device, comprising the steps of:

forming the polyimide resin film according to claim 12 on a support;

forming a display device, a light receiving device, or a sensor member on the polyimide resin film; and

and a step of peeling the polyimide resin film from the support.

18. The method for manufacturing an electronic device according to claim 17, wherein the electronic device is a display device, a light receiving device, or a sensor component.