JP2018016787A - Polyimide composition, polyimide film and polyimide laminate obtained from the polyimide composition, and method for producing polyimide laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide composition that gives a polyimide film that is peelable from a support efficiently and easily, a polyimide laminate having a resin layer obtained from the polyimide composition, and a method for producing a polyimide laminate.SOLUTION: The present invention provides a polyimide composition containing a heterocyclic compound having a polyimide precursor and/or a polyimide and a hydrogen-bonding substituent; a polyimide laminate having a resin layer obtained from the polyimide composition and a polyimide film obtained from the composition; and a method for producing a polyimide laminate.SELECTED DRAWING: None

Description

  The present invention relates to a polyimide precursor and / or a composition containing polyimide that can provide a polyimide film having excellent peelability. Furthermore, it is related with the polyimide film and polyimide laminated body obtained from this composition. Moreover, it is related with the manufacturing method of a polyimide laminated body.

  Conventionally, polyimides having excellent heat resistance, electrical insulation, wear resistance, chemical resistance, mechanical properties, and the like have been widely used in the fields of electricity, electronic parts, transportation equipment, space, aircraft, and the like.

  Conventionally, as a method for producing a polyimide film, a polyimide precursor solution is applied to a support, a solvent in the solution is removed, the autonomous film is peeled off from the support, and the autonomous film is heated to imidize. A method of producing a polyimide precursor solution after applying it to a support, heating to remove the solvent in the solution, and imidizing the polyimide precursor to obtain an autonomous film and removing it from the support, polyimide A method of applying the solution to a support, removing the solvent in the solution, and peeling off from the support as an autonomous film is used. However, in order to peel the autonomous film from the support, the adhesion between the polyimide precursor film or polyimide film and the support is strong, and peeling is often difficult.

Patent Document 1 discloses a resin paste in which a nonionic fluorosurfactant is blended with polyimide resin, polyamideimide resin, polyamide resin, or the like.
Patent Document 2 discloses a polymer composition for film formation containing an organic siloxane such as silicone varnish, and further discloses that a polyimide film produced from this polymer composition is excellent in peelability from a fluent surface. Has been.

JP 2001-123066 A JP 47-33063 A

However, the polyimide film to which a fluorine-based surfactant is added as in Patent Document 1 is a fluorine-based surfactant that remains in the polyimide film, for example, when wiring on a polyimide film or when a device is laminated. The agent tends to inhibit the adhesion between the wiring or upper layer and the polyimide film, leading to defects.
Further, when the upper layer laminating step or the like is at a temperature higher than the polyimide film manufacturing temperature, the fluorosurfactant remaining in the polyimide film during the laminating step can be an outgas and become a factor that hinders the laminating step.
On the other hand, according to the study by the present inventors, when a polyimide film is produced using a film-forming polymer composition containing an organic siloxane such as a silicone varnish as in Patent Document 2, a sufficient peelability is obtained. In addition, a large amount of organosiloxane must be added, and the produced polyimide film may be whitened, that is, it is difficult to achieve both the peelability of the polyimide film and the appearance such as transparency and haze. I understand.

  As a result of intensive studies in view of the above, the present inventors have been able to solve the above problems and support by using a polyimide composition containing a polyimide precursor and / or a polyimide and a heterocyclic compound having a hydrogen bonding substituent. It has been found that a polyimide film that can be easily and efficiently peeled from the body can be obtained.

The present invention relates to the following items.
[1] A polyimide composition comprising a polyimide precursor and / or a polyimide and a heterocyclic compound having a hydrogen bonding substituent.
[2] The polyimide composition according to [1], wherein the heterocyclic compound having a hydrogen bonding substituent has a polarizability of 60 × 10 ⁻²⁵ cm ³ or more.
[3] The polyimide composition according to [1] or [2], wherein the number of heteroelements forming the heterocyclic ring of the heterocyclic compound having a hydrogen bonding substituent is one.
[4] Any of [1] to [3], wherein the hydrogen-bonding substituent of the heterocyclic compound having a hydrogen-bonding substituent is a substituent that can polarize within the substituent and form a hydrogen bond between molecules. The polyimide composition as described in any one.
[5] The polyimide composition according to any one of [1] to [4], wherein the substitution position of the hydrogen bonding substituent of the heterocyclic compound having a hydrogen bonding substituent is β-position or γ-position.
[6] The polyimide composition according to any one of [1] to [5], wherein the polyimide precursor and / or the polyimide is colorless and transparent.
[7] The polyimide composition according to any one of [1] to [6], wherein the polyimide precursor and / or the polyimide has an alicyclic skeleton.
[8] A polyimide laminate having a resin layer obtained from the polyimide composition according to any one of [1] to [7].
[9] A polyimide film obtained from the polyimide composition according to any one of [1] to [7].
[10] A step of obtaining a resin layer using a polyimide composition containing a polyimide precursor and / or a polyimide and a heterocyclic compound having a hydrogen bonding substituent,
Heating the resin layer above the glass transition temperature of the polyimide resin in the resin layer after heating;
The manufacturing method of the polyimide laminated body which has this.

  The film obtained from the polyimide composition of the present invention can be easily and efficiently peeled from the support.

Embodiments of the present invention will be described in detail below, but the following examples and methods are examples (representative examples) of the embodiments of the present invention, and the present invention is not limited to these unless they depart from the gist of the present invention. It is not limited to the contents.
Hereinafter, a composition containing a polyimide precursor and / or polyimide is referred to as a polyimide composition. In addition, a laminate obtained by applying the polyimide composition of the present invention to a substrate to form a resin layer is obtained by applying a polyimide laminate, a polyimide composition on a support, and further peeling from the support. This film is referred to as a polyimide film.

  The polyimide resin composition of the present invention includes a polyimide precursor and / or a polyimide and a heterocyclic compound having a hydrogen bonding substituent.

[Heterocyclic compound having a hydrogen bonding substituent]
(Hydrogen bonding substituent)
In the present invention, the hydrogen-bonding substituent is a substituent that can polarize within a substituent and form a hydrogen bond between molecules, or a substituent that includes an atom having an unshared electron pair. The former includes, for example, a substituent in which hydrogen is bonded to a large electronegativity atom such as sulfur, oxygen, and nitrogen, and the latter includes a substituent composed of a halogen atom.
Specific examples of the hydrogen bonding substituent include a halogen group, a hydroxy group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, Examples include a thioester group, an aldehyde group, and an acetyl group.
When the heterocyclic compound has a hydrogen-bonding substituent, a hydrogen bond is formed between the surface of the support such as glass or metal, and the polyimide precursor or polyimide. Therefore, many heterocyclic compounds can exist at the interface between the support and the polyimide precursor or polyimide. Therefore, the hydrogen bond between the support and the polyimide precursor or polyimide is reduced, and when the polyimide composition of the present invention is used as a film, the peelability from the support is enhanced.

  Although there is no restriction | limiting in particular as a hydrogen bondable substituent, Since the substituent which can polarize in a substituent and can form a hydrogen bond between molecules does not inhibit the adhesiveness of a film surface, it is preferable.

  The substitution position of the hydrogen bonding substituent is not particularly limited, but it is easier to form an intermolecular hydrogen bond when substituted at a position away from the complex element. Are preferably substituted, more preferably substituted at the γ-position.

(Heterocyclic compound having a hydrogen bonding substituent)
There is no restriction | limiting in particular as a kind of heterocyclic ring of the heterocyclic compound which has a hydrogen bondable substituent. The heterocyclic ring may be a monocyclic ring or a condensed ring, and may be composed of a saturated hydrocarbon or an unsaturated hydrocarbon.
Moreover, the polyimide resin composition of the present invention may contain a plurality of heterocyclic compounds having a hydrogen bonding substituent.
In the present invention, among the elements constituting the heterocyclic ring, elements other than carbon elements are referred to as complex elements. The complex element is not particularly limited, but is preferably at least one of nitrogen, oxygen, and sulfur. Among these, it is preferable to have a nitrogen element because the film is less colored and the storage stability of the composition tends to be maintained.
In particular,
A heterocyclic ring containing nitrogen and composed of saturated hydrocarbons;
Heterocycle having one nitrogen element such as ethyleneimine, cyclobutane, pyrrolidine, piperidine, hexamethyleneimine and having an unsaturated bond;
A heterocyclic ring having two or more nitrogen elements such as azirine, azeto, pyrrole, pyridine, azatopyridene, indole, isoindole, quinoline, isoquinoline, carbazole;
Heterocycle composed of saturated hydrocarbons with oxygen elements such as imidazole, pyrazole, imidazoline, pyrazine, benzimidazole, purine, quinoxaline, cinnoline, pteridine, etc .;
Heterocycle having one oxygen element such as ethylene oxide, oxetane, tetrahydrofuran, tetrahydropyran, hexamethylene oxide and the like, and having an unsaturated bond;
Heterocycles composed of saturated hydrocarbons with sulfur elements such as acetylene oxide, oxetium ions, furan, pyrylium ions, oxycycloheptatriene, chromene, isochromene;
Heterocycles having an elemental sulfur bond such as ethylene sulfide, trimethylene sulfide, tetrahydrothiophene, tetrahydrothiopyran, hexamethylene sulfide and the like;
A heterocycle having a plurality of types of heteroelements such as acetylene sulfide, thietium ion, thiophene, thiapyran, tiotropylidene;
Examples include oxazole, benzoxazole, thiazole, benzothiazole, morpholine, thiazine and the like.

  The number of heteroelements contained in the heterocyclic compound is not particularly limited, but is preferably 3 or less, more preferably 1 or 2, and even more preferably 1. By being in the above-mentioned range, the film is less colored and the storage stability of the composition tends to be maintained.

  Examples of the compound having one heteroelement forming a heterocycle include, for example, 4-aminopyridine, 4-dimethylaminopyridine, 4-hydroxypyridine, 4-aminopyridine, wherein the heteroelement is nitrogen and the heterocycle is a monocycle. Pyridinecarboxaldehyde, 4-acetylpyridine, 4-fluoropyridine, 4-pyridinemethanol, 4- (2-aminoethyl) pyridine, 4-pyridinepropanol, 4-pyridineethanethiol, 4-mercaptopyridine, 4-methoxypyridine, Isonicotinamide, isonicotinic acid, methyl isonicotinate, thioisonicotinic acid, 3-aminopyridine, 3-dimethylaminopyridine, 3-hydroxypyridine, 3-pyridinecarboxaldehyde, 3-acetylpyridine, 3-pyridinemethanol, 3- (2-aminoethyl) pyri , 3-pyridinepropanol, 3-pyridineethanethiol, 3-mercaptopyridine, 3-methoxypyridine, nicotinamide, nicotinic acid, methyl nicotinate, isonicotinic acid, 2-amino-4-methylpyridine, 3-amino-4- Examples include methylpyridine and 3-nitropyrrole. Further, as a compound in which the hetero element forming the hetero ring is one nitrogen element and is a condensed ring, 4-quinoline carboxaldehyde, 7-quinoline carboxaldehyde, 4-quinolinol, 5-quinolinol, 7-quinolinol, 6 -Methoxy-2-methylquinoline, 4-amino-2-methylquinoline, 8-amino-2-methylquinoline, 4-quinolinecarboxylic acid, 5-quinolinecarboxylic acid and the like, wherein the complex element is sulfur, 3-acetylthiophene, 3- Examples include thiophene carboxaldehyde, 3-thiophene methanol and the like.

  Examples of the compound having 2 or more heteroelements forming a heterocyclic ring include 4-imidazole carboxaldehyde, 4-imidazolecarboxylic acid, ethyl 4-imidazolecarboxylate, 4,5-bis (hydroxymethyl) imidazole, 2-acetylpyrazine, Examples include 2-pyrazinemethanol and 2-aminomethyl-5-methylpyrazine.

The heterocyclic compound having a hydrogen bonding substituent is not particularly limited, but the average polarizability of the molecule is preferably 60 × 10 ⁻²⁵ cm ³ or more, more preferably 80 × 10 ⁻²⁵ cm ³ or more, and 100 ×. More preferably, it is 10 ⁻²⁵ cm ³ or more. A higher average polarizability of the molecule is preferable because hydrogen bondability is increased.
The average polarizability of the molecule can be obtained from the Lorentz Lawsen equation.

  The volatilization temperature of the heterocyclic compound having a hydrogen bonding substituent is not particularly limited, but is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and even more preferably 250 ° C. or lower because residual in the polyimide film decreases. . Moreover, although a minimum is not specifically limited, For example, it is 60 degreeC or more.

  The concentration of the heterocyclic compound having a hydrogen bonding substituent in the polyimide composition is not particularly limited, but is usually 0.01% by mass or more, preferably with respect to the polyimide precursor and / or polyimide contained in the composition. It is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. Moreover, it is 20 mass% or less normally, Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less. When the amount of the heterocyclic compound having a hydrogen bonding substituent is within this range, it is preferable because good release properties can be obtained and the storage stability of the composition tends to be good.

  The concentration of the heterocyclic compound having a hydrogen bonding substituent can be analyzed by a conventionally known method. For example, nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR), liquid chromatography (LC), gas chromatography (GC), mass spectrometry (MS), time-of-flight secondary ions Examples thereof include mass spectrometry (TOF-SIMS), a method combining these, and the like.

[Polyimide precursor and / or polyimide]
The polyimide precursor of this invention has a polyamic acid and / or a polyamic acid ester. Moreover, a part of polyimide precursor may have a polyimide structure, and polyamic acid and / or polyamic acid ester and polyimide may be mixed.
The polyimide of the present invention has a polyimide structure and does not substantially contain a polyamic acid and / or a polyamic acid ester.

The polyimide precursor and / or polyimide of the present invention may be a block copolymer. For example, a combination of a polyimide block and a polyimide precursor block, a combination of a polyimide block and a polyimide block, a combination of a polyimide precursor block and a polyimide precursor block, and the like can be given.
Further, the polyimide precursor and / or polyimide of the present invention may be one kind or may contain plural kinds. These are not necessarily synthesized under the same reaction conditions, the same imidization rate, and the same solubility in a solvent, and may be adjusted under different conditions and may have different physical properties. In the present invention, the molecular weight described below represents the average value of the polyimide precursor and / or polyimide contained in the composition.

  The structure of the polyimide precursor and / or polyimide of the present invention is not particularly limited. For example, a unit (tetracarboxylic acid residue) derived from a tetracarboxylic dianhydride compound that is a raw material of the polyimide precursor and / or polyimide described below. And a structure having a unit (diamine residue) derived from a diamine compound and a diisocyanate compound.

  The polyimide precursor and / or polyimide of the present invention are not particularly limited as long as they are soluble in a solvent, but those having high solubility are preferable because the resulting polyimide film becomes colorless and transparent. In the present invention, being colorless and transparent means that the transmittance of light of 500 nm is 70% or more when the film thickness is 1 to 300 μm. The transmittance is more preferably 80% or more, and still more preferably 85% or more. Here, the transmittance means the total light transmittance at 500 nm according to JIS K 7136-1.

  Among them, the polyimide precursor and / or polyimide of the present invention preferably has an aliphatic skeleton because of excellent solubility, and further preferably has an alicyclic structure. In addition, the position of the aliphatic skeleton and the alicyclic structure is not particularly limited, but the polyimide precursor and / or the unit derived from the tetracarboxylic dianhydride that is a raw material of the polyimide may have the polyimide precursor and / or It is preferable because it is easy to produce polyimide and it is easy to control the viscosity of the composition.

  In the present invention, “soluble in a solvent” means that the polyimide precursor and / or polyimide is dissolved at room temperature (25 ° C.) in the solvent used for the polyimide precursor and / or polyimide composition of the present invention. In some cases, it dissolves completely. The concentration for complete dissolution is usually 0.5% by mass or more, preferably 1% by mass or more, and more preferably 10% by mass or more.

  The weight average molecular weight (Mw) of the polyimide precursor and / or polyimide is not particularly limited. The weight average molecular weight in terms of polystyrene is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150,000 or less. By being in this range, the solubility in a solvent, the composition viscosity and the like tend to be easily handled with ordinary production equipment, which is preferable. The polystyrene-reduced weight average molecular weight can be determined by gel permeation chromatography (GPC).

  The number average molecular weight (Mn) of the polyimide precursor and / or polyimide is not particularly limited. The number average molecular weight in terms of polystyrene is usually 500 or more, preferably 1000 or more, more preferably 2500 or more. Further, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in this range, the solubility in a solvent, the composition viscosity and the like tend to be easily handled with ordinary production equipment, which is preferable. The number average molecular weight in terms of polystyrene can be determined by the same method as the weight average molecular weight.

  The molecular weight distribution (PDI: weight average molecular weight / number average molecular weight (Mw / Mn)) of the polyimide precursor and / or polyimide is usually 1 or more, preferably 1.1 or more, more preferably 1.2 or more. Moreover, it is 10 or less normally, Preferably it is 9 or less, More preferably, it is 8 or less. By being in this range, a film excellent in uniformity and smoothness of components in the film tends to be obtained.

<Tetracarboxylic dianhydride to induce tetracarboxylic acid residue>
Examples of the tetracarboxylic dianhydride include an aromatic ring-containing tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, and a silicone-based tetracarboxylic dianhydride.

(Tetracarboxylic dianhydride having an aromatic ring)
As tetracarboxylic dianhydride having an aromatic ring, tetracarboxylic dianhydride having one aromatic ring contained in one molecule, tetracarboxylic acid having two or more independent aromatic rings in one molecule Examples of dianhydrides include tetracarboxylic dianhydrides having a condensed aromatic ring in one molecule. Among these, since the viscosity at the time of production is easy to control, tetracarboxylic dianhydride in which one aromatic ring is contained in one molecule or tetracarboxylic acid having two or more independent aromatic rings in one molecule Acid dianhydrides are preferable, and tetracarboxylic dianhydrides having two or more independent aromatic rings in one molecule are particularly preferable. Examples of the tetracarboxylic dianhydride having one aromatic ring in one molecule include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride. .

Examples of tetracarboxylic dianhydrides having two or more independent aromatic rings in one molecule include 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3- Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4 -Dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3 3'-Ben Phenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic acid Anhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoro Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylene) -diphthalic dianhydride, 4,4 '-(octafluorotetramethylene) -diphthal Acid dianhydride, 4,4'-oxydi Talic anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2′-bis (trifluoro Methyl) -4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride, 4,4 ′-(hexafluorotrimethylene) -diphthalic dianhydride, 4,4 ′-(octafluorotetramethylene) -Diphthalic dianhydride etc. are mentioned.
Among these, from the viewpoint of solubility, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, or 4,4′-oxydiphthalic acid A dianhydride is preferred.

  Examples of tetracarboxylic dianhydrides having a condensed aromatic ring in one molecule include 1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic dianhydride, 2, 3,6,7-naphthalenedicarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7 , 8-phenanthrenetetracarboxylic dianhydride and the like.

(Aliphatic tetracarboxylic dianhydride)
Examples of the aliphatic tetracarboxylic dianhydride include alicyclic tetracarboxylic dianhydrides and chain aliphatic tetracarboxylic dianhydrides. Among these, alicyclic tetracarboxylic dianhydrides are preferable.

Examples of the alicyclic tetracarboxylic dianhydride include 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tricyclo [6.4.0.0 (2 7)] dodecane-1,8: 2,7-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, Examples include 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride, and the like.
Among the alicyclic tetracarboxylic dianhydrides, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride or 1,2,4,5-cyclohexyltetracarboxylic dianhydride is This is preferable because the solubility of the polyimide precursor and / or polyimide is improved and a film having excellent dimensional stability tends to be obtained.

  Examples of the chain aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, etc. Is mentioned.

(Silicon tetracarboxylic dianhydride)
Examples of the silicon-based tetracarboxylic dianhydride include those represented by the following general formula (1).

In general formula (1), X is an organic group containing an acid anhydride structure, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a substituent. It may be an alkyl group or a phenyl group, and n ¹ is an integer of 3 to 200.

<Diamine compound that induces a diamine residue>
Examples of the diamine compound include aromatic diamine compounds, aliphatic diamine compounds, silicone diamine compounds and the like. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

(Aromatic diamine compound)
As an aromatic diamine compound, a diamine compound having one aromatic ring in one molecule, a diamine compound having two or more independent aromatic rings in one molecule, a diamine compound having a condensed aromatic ring in one molecule, etc. Is mentioned. Among these, a diamine compound having one aromatic ring in one molecule or a diamine compound having two or more independent aromatic rings is preferable in terms of facilitating viscosity control during production. Particularly preferred are diamine compounds having the following aromatic rings.

  Examples of the diamine compound having one aromatic ring in one molecule include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, and the like.

  Examples of the diamine compound having two or more independent aromatic rings in one molecule include 4,4 ′-(biphenyl-2,5-diylbisoxy) bisaniline, 4,4′-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis ( 4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) ) Neopentane, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino-2,2′-dimethylbiphenyl Enyl, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane, 4,4′-diamino Diphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamine, 2,2′-bis (trifluoromethyl) -4, 4′-diaminobiphenyl, bis (3-aminophenyl) sulfone, norbornanediamine, 4,4′-diamino-2- (trifluoromethyl) diphenyl ether, 5-trifluoromethyl-1,3-benzenediamine, 2,2 -Bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4,4'-dia No-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 2-trifluoromethyl-p -Phenylenediamine, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane and the like.

  Among these, from the viewpoint of solubility, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, (4- (4-aminophenoxy) phenyl) sulfone, 4,4′-diaminodiphenyl sulfone, 3, 3'-diaminodiphenyl sulfone, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and the like are preferable.

  Examples of the diamine compound having a condensed aromatic ring in one molecule include 4,4 '-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 1,5-diaminonaphthalene, 3,7-diamino-2,8- Examples include dimethyldibenzothiophene 5,5-dioxide.

(Aliphatic diamine compound)
Examples of the aliphatic diamine compound include alicyclic diamine compounds and chain aliphatic diamine compounds.
Examples of the alicyclic diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine) and the like.

Examples of chain aliphatic diamine compounds include (1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1, 5-diaminopentane, 1,10-diaminodecane, 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butanediamine, 2-methyl-1,5-diaminopentane) and the like. It is done.
Among these, from the viewpoint of solubility, alicyclic diamine compounds are preferable, and 1,4-diaminocyclohexane or 1,3-bis (aminomethyl) cyclohexane is particularly preferable.

(Silicone-based diamine compounds)
Examples of the silicone-based diamine compound include those represented by the following general formula (2).

In general formula (2), R ⁵ and R ⁶ are each independently a divalent organic group, and R ⁷ and R ⁸ are each independently an alkyl group or a phenyl group which may have a substituent. , N ² is 3 to ²
It is an integer of 00.

<Diisocyanate compound that induces a diamine residue>
Examples of the diisocyanate compound include an aromatic skeleton having an aliphatic skeleton, such as hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane. 3,3′-dichloro-4,4′-diisocyanate biphenyl, 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 1,5-diisocyanate naphthalene, methylenediphenyl 4,4-diisocyanate, 1,3- Examples include phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, and m-xylylene diisocyanate.

<Tetracarboxylic acid residue and / or diamine residue having a bent portion>
In the polyimide precursor and / or polyimide in the composition of the present invention, having a tetracarboxylic acid residue and / or diamine residue having a bent portion improves the solubility of the polyimide precursor and / or polyimide in the solvent. And is preferred because it tends to suppress moisture absorption whitening and baking whitening. Moreover, it is preferable because the optical properties of the obtained film tend to be improved.
In the present invention, the bending portion is a bending portion in which deformation is suppressed, and a ring bond angle around the bending portion, a ring surface angle bonded to the bending portion, a tetracarboxylic acid residue such as rotation, vibration, etc. And / or the thing which suppresses the movement of the molecule | numerator containing a diamine residue. Among them, those that suppress the ring coupling angle and rotational movement around the bent portion are preferable.

That is, the bent portion is preferably a trivalent or higher group that is directly bonded to the ring structure and the ring structure, and the bond angle between the ring structures is less than 180 degrees, preferably 160 degrees or less, more preferably 130 degrees. It is as follows. There is no particular lower limit, but it is usually 90 degrees or more.
The angle can be obtained by a conventionally known calculation method. For example, empirical molecular orbital methods such as Hückel method and extended Huckel method, Hartley Fock method, configuration interaction method, ab initio molecular orbital methods such as multi-substitution SCF method, PPP approximation, CNDO / 2, INDO, MNDO And semi-empirical molecular orbital methods such as AMI and PM3, molecular dynamics methods such as MM2, and density functional methods such as BLYP and B3LYP.

In the present invention, by having a bent portion, thermal vibration of the polyimide precursor and / or the entire polyimide chain is suppressed, and the linear expansion coefficient tends to be improved. Furthermore, since the interaction between the polyimide precursor and / or the polyimide chain is suppressed, the solubility in a solvent tends to be improved. In addition, the optical properties of the obtained film tend to be improved, and the retardation tends to be improved by disrupting the regular alignment of the same chain.
Further, the entanglement of molecular chains of the polyimide precursor and / or polyimide increases, and the amount of aromatic rings in the chain increases, whereby the heat resistance tends to be improved.

  As described above, the polyimide precursor and / or polyimide in the composition of the present invention preferably has a tetracarboxylic acid residue and / or a diamine residue having a bent portion, and in particular, is soluble in a solvent. It is preferable that the diamine residue has a bent portion because the optical properties tend to be improved and the optical properties tend to be improved. In addition, it is also preferable that the tetracarboxylic acid residue and the diamine residue have a bent portion because the optical properties tend to be improved.

In the present invention, the tetracarboxylic acid residue and / or diamine residue may have a plurality of bending sites, but it is preferable that the plurality of bending sites are not connected. It exists in the tendency which can maintain and improve polymerizability because the bending part is not connected.
In the present invention, it is preferable that a cyclic structure is directly bonded to the bent portion. By directly bonding the annular structure, deformations such as a bonding angle, a surface angle of a ring bonded to a bent portion, rotation, vibration, and the like are further suppressed. The cyclic structure directly bonded to the bending site may be derived from the same tetracarboxylic acid residue / diamine residue as the bending site or may be different. When derived from the same tetracarboxylic acid residue / diamine residue as that of the bent part, the cyclic structure is a structure possessed by the tetracarboxylic acid monomer / diamine monomer. When not derived from the same tetracarboxylic acid residue / diamine residue as the bending site, the cyclic structure is a cyclic imide structure.

  The amount of the bent portion introduced is not particularly limited, but is usually 0.1 mol% or more, preferably 0.5 mol% or more, in a ratio to the sum of tetracarboxylic acid residues and / or diamine residues in the composition. More preferably, it is 1 mol% or more, More preferably, it is 5 mol% or more. Moreover, it is 150 mol% or less normally, Preferably it is 100 mol% or less, More preferably, it is 50 mol% or less. By being in these ranges, solubility in a solvent is improved, and moisture absorption whitening and fired whitening tend to be suppressed. In addition, the optical characteristics are good, and the mechanical characteristics tend to be improved.

As a bending part, it is preferable that the element which comprises a principal chain couple | bonded with the ring has a trivalent or more bond. Among the trivalent or higher bonds, at least one selected from a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine, and a benzene ring is preferable. In particular, a tetracarboxylic residue and / or a diamine residue having a bending site is one in which two or more aromatic rings are bonded to each other by a quaternary carbon atom and / or a hexavalent sulfur atom. It is preferable because the optical properties tend to be improved and the optical properties are further improved.
Those having a bond of 3 or more are not particularly limited as long as they do not depart from the gist of the present invention.

In the general formula (3), Z ¹ represents a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine, or a benzene ring. Y ¹ and Y ² each independently represent a cyclic structure.
As the quaternary carbon, hexafluoropropane, propane, fluorene and the like are preferable because they tend to improve optical characteristics and heat resistance. As hexavalent sulfur, a sulfonyl group is preferable because it tends to improve optical properties. Trimethylamine is preferred as the tertiary amine.

The cyclic structure of Y ¹ and Y ² represents an aromatic compound, an alicyclic compound, or an imide ring.
With the aromatic compound, the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a condensed aromatic ring or a heterocyclic ring.
The number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
The heterocyclic ring is not particularly limited, and specific examples include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
Examples of the substituent that the aromatic compound may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a hydroxyl group.
The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may have a substituent.
Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
Examples of the substituent that the alkoxy group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.

The alicyclic compound has 4 or more and 8 or less carbon atoms forming one ring, and a single ring or two rings may be condensed. Moreover, you may have an unsaturated bond in the ring.
Specific examples include cyclobutane, cyclobutadiene, cyclopentane, cyclopentaene, cyclohexane, cyclohexaene, cyclohexadiene, cycloheptane, cycloheptaene, cyclooctane, and the like.
The alicyclic compound may have a substituent, and examples of the substituent that may be included include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino group. Group, hydroxyl group and the like. The alkyl group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 6 or less carbon atoms may have a substituent. Is synonymous with

An imide ring is a ring having an imide bond, and the number of elements forming one ring is 4 or more and 6 or less. Only an imide ring may be sufficient and it may be condensed with another ring. The ring which may be condensed is an aromatic compound and / or an alicyclic compound. The number of rings in the case of condensation is not particularly limited, but is preferably 2 or more and 4 or less because heat resistance and optical properties tend to be compatible.
The aromatic compound and the alicyclic compound may have a substituent, and specifically have the same meaning as those mentioned for the aromatic compound.

  Among the structures represented by the general formula (3), a site selected from the structures represented by the following general formulas (4) to (8) is preferable from the viewpoint of improving optical properties.

In General Formula (4), R ¹⁰ and R ¹¹ each independently represent an alkyl group, an amino group, or a hydroxyl group, and Y ¹ and Y ² each independently represent a cyclic structure.
The alkyl group for R ¹⁰ and R ¹¹ preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low. Moreover, the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, unsubstituted or preferably having a halogen atom is preferable, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Y ¹ and Y ² in the general formula (4) has the general formula (3) have the same meanings as Y ¹ and Y ^2, specific examples, preferred ranges, and the substituent which may have also the same.

In the general formula (5), R ^{12 to} R ¹⁵ each independently represents an alkyl group or a hydroxyl group, and Y ¹ and Y ² each independently represent a cyclic structure.
The alkyl group of R ^{12 to} R ¹⁵ preferably has 1 or more carbon atoms. On the other hand, the carbon number is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less. This range is preferable because the linear expansion coefficient tends to be low. Moreover, the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, it is preferable to have a halogen atom, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Y ¹ and Y ² in the general formula (5) has the general formula (3) have the same meanings as Y ¹ and Y ^2, specific examples, preferred ranges, and the substituent which may have also the same.

In General Formula (6), Y ¹ and Y ² each independently represent a cyclic structure.
Y ¹ and Y ² in the general formula (6) has the general formula (3) have the same meanings as Y ¹ and Y ^2, specific examples, preferred ranges, and the substituent which may have also the same.

In General Formula (7), R ¹⁶ represents an alkyl group or an aromatic compound, and Y ¹ and Y ² each independently represent a cyclic structure.
Y ¹ and Y ² in the general formula (7) is general formula (3) have the same meanings as Y ¹ and Y ^2, specific examples, preferred ranges, and the substituent which may have also the same.
The alkyl group for R ¹⁶ preferably has 1 or more carbon atoms. On the other hand, the carbon number is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less. This range is preferable because the linear expansion coefficient tends to be low. Moreover, the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, it is preferable to have a halogen atom, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.

In the aromatic compound of R ^16, the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a condensed aromatic ring or a heterocyclic ring. Among these, a monocyclic benzene ring and a condensed aromatic ring obtained by condensing a benzene ring are preferable because the linear expansion coefficient tends to be low.
The number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical characteristics tend to be compatible.

The heterocyclic ring is not particularly limited, and specific examples include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
Examples of the substituent that the aromatic compound may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a hydroxyl group.
The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may have a substituent.
Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
Examples of the substituent that the alkoxy group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.

In the general formula (8), R ¹⁷ represents an alkyl group, a nitro group, an amino group, a hydroxyl group or a halogen atom.

The alkyl group is not particularly limited, but preferably has 1 or more carbon atoms. On the other hand, the carbon number is preferably 8 or less, and more preferably 5 or less. By being in these ranges, the compatibility with the solvent tends to be improved.
The alkyl group may have a substituent, and examples thereof include an amino group, a hydroxyl group, a nitro group, and a halogen atom.

  Examples of the diamine residue having the structure represented by the general formula (8) include 2,6-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 2, 3-diaminotoluene, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 2 -Nitro-1,2-phenylenediamine, 3-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 3 -Hydroxy-1,5-phenylenediamine, 4-hydroxy-1,5-phenylenediamine, 4-hydroxy-1,2- Derived diamine residue from a diamine compound such Enirenjiamin like.

  Examples of the tetracarboxylic acid residue in which two or more aromatic rings are bonded by a quaternary carbon atom include 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 4,4′-isopropyl acetate. Redene diphthalic anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3 A tetracarboxylic acid residue derived from a tetracarboxylic dianhydride such as -dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  Examples of tetracarboxylic acid residues in which two or more aromatic rings are bonded by a hexavalent sulfur atom include 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3, and the like. ', 4'-Diphenylsulfonetetracarboxylic dianhydride, 2,2', 3,3'-diphenylsulfonetetracarboxylic dianhydride, 4,4 '-[p-sulfonylbis (phenylenesulfanyl)] diphthalic acid Examples include tetracarboxylic acid residues derived from tetracarboxylic dianhydrides such as anhydrides and 3,3 ′-[p-sulfonylbis (phenylenesulfanyl)] diphthalic anhydride.

  Examples of the diamine residue in which two or more aromatic rings are bonded by a quaternary carbon atom include 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) hexa. Fluoropropane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminopheni) -2-propyl] benzene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) propane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (2-aminophenyl) Fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- From diamine compounds such as {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane and 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} hexafluoropropane Derived diamine residues are mentioned.

  Examples of the diamine residue in which two or more aromatic rings are connected by a hexavalent sulfur atom include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, and 3,4′-diaminodiphenylsulfone. 4,4′-bis (4-aminophenylenesulfanyl) diphenylsulfone, 3,3′-bis (4-aminophenylenesulfanyl) diphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4 Derived from diamine compounds such as-(3-aminophenoxy) phenyl] sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 3,3 ', 4,4'-tetraaminodiphenylsulfone A diamine residue is mentioned.

[Production method of polyimide precursor]
The polyimide precursor of the present invention is obtained by reacting a tetracarboxylic dianhydride with a diamine compound and / or a diisocyanate compound in a solvent. The method for reacting tetracarboxylic dianhydride in a solvent is not particularly limited. Moreover, the addition order and addition method of a tetracarboxylic dianhydride and a diamine compound are not particularly limited. For example, a polyimide precursor can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.

  The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. is there. By making a diamine compound into this range, it exists in the tendency for the yield of the polyimide precursor obtained to improve.

The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the obtained polyimide precursor.
The total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, based on the total amount of the solution containing the tetracarboxylic dianhydride, the diamine compound and the solvent. It is usually 70% by mass or less, preferably 50% by mass or less. Since the concentrations of the tetracarboxylic dianhydride and the diamine compound are not too low, the molecular weight tends to increase. In addition, by not being too high, the viscosity does not become too high and the solution tends to be easily stirred.

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted in the solvent is not particularly limited as long as the reaction proceeds, but is usually 0 ° C or higher, preferably 20 ° C or higher, and usually 120 ° C or lower. The temperature is preferably 100 ° C. or lower.
The reaction time is usually 1 hour or longer, preferably 2 hours or longer, usually 100 hours or shorter, preferably 42 hours or shorter. By carrying out under such conditions, the polyimide precursor tends to be obtained at a low cost and in a high yield.
The pressure during the reaction may be normal pressure, pressurization, or reduced pressure. The atmosphere may be air or an inert atmosphere.

  The solvent used when making tetracarboxylic dianhydride and a diamine compound react is not specifically limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; halogenated carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, fluorobenzene, etc. Hydrocarbon solvents; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol solvents such as glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; N, N Amide solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; sulfone solvents such as dimethyl sulfoxide; heterocyclic solvents such as pyridine, picoline, lutidine, quinoline, isoquinoline; phenol, cresol Phenol solvents such as γ-butyrolactone, γ-valerolactone, lactone solvents such as δ-valerolactone, and the like. These solvents may be used alone or in combination of two or more in any ratio and combination.

(Reprecipitation and re-dissolution of polyimide precursor)
The obtained polyimide precursor may be used as it is, or may be added to a poor solvent to precipitate in a solid state, and then redissolved in another solvent to obtain a polyimide precursor composition.
The poor solvent to be used is not particularly limited and may be appropriately selected depending on the type of the polyimide precursor, but ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; methanol, And alcohol solvents such as ethanol and isopropyl alcohol. Among these, alcohol solvents are preferable because precipitates can be obtained efficiently, the boiling point is low, and drying tends to be easy. These solvents may be used alone or in combination of two or more in any ratio and combination.

[Production method of polyimide]
There is no restriction | limiting in particular in the manufacturing method of the polyimide contained in the composition of this invention. For example, the method of manufacturing a polyimide precursor and obtaining a polyimide, the method of manufacturing a polyimide directly from a tetracarboxylic dianhydride, a diamine compound, and / or a diisocyanate compound, etc. can be used.

<Method of manufacturing from polyimide precursor>
A polyimide can be obtained by dehydrating and cyclizing (imidizing) the polyimide precursor obtained by the above method in the presence of a solvent. Although imidation can be performed using any conventionally known method, for example, thermal imidization for thermal cyclization, chemical imidization for chemical cyclization, and the like can be given. These imidation reactions may be performed alone or in combination.

(Heat imidization)
Examples of the solvent for imidizing the polyimide precursor include the same solvents as those used in the reaction for obtaining the polyimide precursor. The solvent at the time of manufacturing the polyimide precursor and the solvent at the time of manufacturing the polyimide may be the same or different.
In this case, water generated by imidization may be discharged out of the system in order to inhibit the ring closure reaction. The concentration of the polyimide precursor during the imidation reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. By carrying out in this range, the production efficiency tends to be high and the solution viscosity tends to be easy to produce.

The imidation reaction temperature is not particularly limited, but is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. Performing in this range is preferable because the imidization reaction proceeds efficiently and reactions other than the imidization reaction tend to be suppressed.
The pressure during the reaction may be normal pressure, pressurization, or reduced pressure. The atmosphere may be air or an inert atmosphere.

In addition, as an imidization accelerator for promoting imidization, a compound having a function of enhancing nucleophilicity and electrophilicity can be added. Specifically, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine Tertiary amine compounds such as N-methylpiperidine, N-ethylpiperidine, pyridine, quinoline and isoquinoline; carboxylic acid compounds such as 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, N-acetylglycine and N-benzoylglycine; Polyhydric phenol compounds such as 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, pyrogallol, methyl gallate, ethyl gallate, naphthalene-1,6-diol, pyridine, quinoline, isoquino Emissions, phenanthroline, 1,10-phenanthroline, imidazole, benzimidazole, heterocyclic compounds such as 1,2,4-triazole; and the like.
Etc.

  Among these, at least one selected from the group consisting of tertiary amine compounds, carboxylic acid compounds and heterocyclic compounds is preferable, and at least one selected from the group consisting of triethylamine, imidazole and pyridine controls the imidization rate. It is more preferable because it tends to be easy to do. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

The amount of the imidization accelerator used is usually 0.01 mol or more, preferably 0.1 mol% or more, and more preferably 1 mol% or more with respect to the carboxyl group or ester group. Moreover, it is preferable that it is 50 mol% or less, and it is more preferable that it is 10 mol% or less. When the usage-amount of a catalyst exists in the said range, it exists in the tendency for the imidation reaction to advance efficiently and to obtain the polyimide which controlled the imidation ratio.
Moreover, the timing which adds an imidation promoter can be adjusted suitably in order to make it a desired imidation rate, may be before a heating start, and may be during a heating. Moreover, you may add in multiple times.

(Chemical imidization)
A polyimide can be obtained by chemically imidizing a polyimide precursor using a dehydration condensing agent in the presence of a solvent.
Examples of the solvent used in the chemical imidization include the same solvents as those used in the reaction for obtaining the polyimide precursor.

  Examples of the dehydrating condensing agent include N, N-2-substituted carbodiimides such as N, N-dicyclohexylcarbodiimide and N, N-diphenylcarbodiimide; acid anhydrides such as acetic anhydride and trifluoroacetic anhydride; thionyl chloride and tosyl chloride and the like. Chlorides of: acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobuty Ryl fluoride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di-, tri Bromoacetyl chloride, mono-, di-, tri-iodoacetyl chloride, mono-, di-, tri-fluoroacetyl chloride, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyl iodide, thionyl fluoride Halide compounds such as rides; Phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, and cyanide diethyl phosphate; and the like.

  Among these, acid anhydrides and / or halogenated compounds are preferred, and in particular, acid anhydrides tend to allow the imidization reaction to proceed efficiently and to obtain a polyimide with a controlled imidization rate. Therefore, it is more preferable. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

  The amount of these dehydrating condensing agents used is usually 0.1 mol or more, preferably 0.2 mol or more, and usually 1.0 mol or less, preferably 0.9 mol or less, relative to 1 mol of the polyimide precursor. By setting the dehydration condensing agent within this range, the imidization rate can be controlled.

  Although there is no restriction | limiting in particular in the density | concentration of the polyimide precursor at the time of imidation reaction, Usually, 1 mass% or more, Preferably it is 5 mass% or more, and is 70 mass% or less normally, Preferably it is 40 mass% or less. By setting it within this range, the imidation rate can be controlled, production efficiency tends to be high, and the solution viscosity tends to be easy to manufacture.

The imidization reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher. Moreover, it is 150 degrees C or less normally, Preferably it is 130 degrees C or less, More preferably, it is 100 degrees C or less. It is preferable to carry out in this range since the imidization reaction proceeds efficiently and a polyimide having a controlled imidization rate tends to be obtained. Furthermore, it is preferable because side reactions other than the imidization reaction are suppressed.
The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.

  Further, as a catalyst for promoting imidization, the above-mentioned tertiary amines and the like can be added in the same manner as in the heating imidization.

<Method for producing polyimide from tetracarboxylic dianhydride and diamine compound and / or diisocyanate compound>
A polyimide can be obtained directly from a tetracarboxylic dianhydride and a diamine compound and / or a diisocyanate compound using a conventionally known method. In this method, the synthesis from the synthesis of the polyimide precursor to the imidization is performed without stopping the reaction or isolating the precursor.

  There are no particular limitations on the order and method of addition of tetracarboxylic dianhydride and diamine compound. For example, the temperature at which the reaction until imidization proceeds by sequentially adding tetracarboxylic dianhydride and diamine compound to the solvent. The polyimide is obtained by stirring at.

  The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. By setting the amount of the diamine compound in such a range, it is possible to obtain a polyimide with a controlled imidization rate, and the yield of the resulting polyimide tends to be improved.

  The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set for each condition and the viscosity during polymerization. The total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly set, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably with respect to the total liquid amount. It is 40 mass% or less. When the concentration in the solvent is within an appropriate range, elongation of molecular weight tends to occur, and stirring tends to be facilitated.

Examples of the solvent used in this reaction include the same solvents as those used in the reaction for obtaining the polyimide precursor.
Moreover, also when obtaining a polyimide from a tetracarboxylic dianhydride and a diamine compound, heating imidation and / or chemical imidation can be used similarly to the case where a polyimide is obtained from a polyimide precursor. The reaction conditions for heating imidization and chemical imidization in this case are the same as described above.

(Reprecipitation and re-dissolution of polyimide)
The obtained polyimide may be used as it is, or may be added to a poor solvent so that the polyimide is precipitated in a solid state and then re-dissolved in another solvent.

  The poor solvent used at this time is not particularly limited and may be appropriately selected depending on the type of polyimide. For example, ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; And alcohol solvents such as methanol, ethanol, isopropyl alcohol, and the like. Among them, alcohol solvents such as isopropyl alcohol are preferable because precipitates can be obtained efficiently and the boiling point is low and the drying tends to be easy. These solvents may be used alone or in combination of two or more in any ratio and combination.

Examples of the solvent for re-dissolving polyimide include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, and anisole; N, N-dimethylformamide, N, N-dimethylacetamide, N Amide solvents such as methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; Etc. Among these, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether, and ethylene glycol monomethyl ether are particularly preferable. These solvents may be used alone or in combination of two or more in any ratio and combination.
[Polyimide composition]
<Solvent>
In the polyimide composition of the present invention, a polyimide precursor and / or polyimide is usually dissolved in a solvent. The solvent used in the composition of the present invention is not particularly limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; carbon tetrachloride, methylene chloride, chloroform Halogenated hydrocarbon solvents such as 1,2-dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl Ketone solvents such as ketones; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Glycol solvents such as rumonomethyl ether acetate; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Aprotic polar solvents such as dimethyl sulfoxide; Pyridine and picoline Heterocyclic solvents such as lutidine, quinoline and isoquinoline; phenol solvents such as phenol and cresol; lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone, isopropyl alcohol, butanol, hexanol, 2- Examples include organic solvents such as alcohol solvents such as ethyl-1-hexanol, heptanol, and benzyl alcohol. These solvents may be used alone or in combination of two or more in any ratio and combination.

<Other components of polyimide composition>
The polyimide composition of the present invention can contain other components without departing from the gist of the present invention. Other components include, for example, surfactants, antioxidants, lubricants, colorants, stabilizers, UV absorbers, antistatic agents, flame retardants, plasticizers, mold release agents, leveling agents, antifoaming agents, etc. Is mentioned. Moreover, you may mix | blend inorganic type fillers or organic type fillers, such as a powder form, a granular form, plate shape, or fiber form, as long as the objective of invention is not impaired as needed. These other components may be added at any stage of any process for producing the polyimide precursor and / or polyimide composition.

  Among other components, it is preferable to include a leveling agent because the smoothness of the polyimide film tends to be improved. Examples of the leveling agent include silicone compounds. The silicone compound is not particularly limited. For example, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyether-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified hydroxyl group Examples thereof include polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, highly polymerized silicone, amino-modified silicone, amino-derivative silicone, phenyl-modified silicone, and polyether-modified silicone.

<Method for producing polyimide composition>
There is no restriction | limiting in particular in the manufacturing method of the composition of this invention. For example, a mixed polyimide precursor and / or a method of dissolving a polyimide and a heterocyclic compound having a hydrogen bonding substituent in a solvent, a polyimide precursor and / or a polyimide prepared in a solvent having a hydrogen bonding substituent. Examples thereof include a method of adding a ring compound, a polyimide precursor dissolved in a solvent, and / or a method of adding a heterocyclic compound having a hydrogen bonding substituent to polyimide.

  The concentration of the polyimide precursor and / or polyimide in the composition of the present invention is not particularly limited, but is usually 3% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more. Moreover, it is 60 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 45 mass% or less. When the concentration is within this range, the composition can be easily produced, and the thickness and surface of the film tend to be uniform.

  The concentration of the polyimide precursor and / or polyimide in the composition can be appropriately confirmed using a conventionally known method. For example, the solvent of the composition and other components can be distilled off using a method such as drying under reduced pressure, and the mass ratio before and after the distillation can be obtained.

Although there is no restriction | limiting in particular in the viscosity of the composition of this invention, it is a viscosity of the density | concentration 20% in 25 degreeC, and is 100 cP or more normally, Preferably it is 200 cP or more, More preferably, it is 500 cP or more. Further, it is usually 200000 cP or less, preferably 100000 cP or less, more preferably 80000 cP or less. When the viscosity of the composition is within this range, handling during production becomes easy, and handling during coating becomes easy.
The viscosity of the composition can be measured by a conventionally known method. For example, it can be measured using a vibration viscometer, an E-type viscometer or the like.

[Polyimide laminate]
The laminate of the present invention has a resin layer obtained from the polyimide composition of the present invention. Although the formation method of the resin layer is not limited at times, a method of applying the polyimide composition to a substrate or the like can be mentioned.
Examples of the application method include die coating, spin coating, screen printing, spraying, a casting method, a method using a coater, a coating method by spraying, a dipping method, a calendar method, and a fluency method. These methods can be appropriately selected according to the application area, the shape of the surface to be applied, and the like.

The method for volatilizing the solvent contained in the resin layer formed by coating or the like is not particularly limited. Usually, a solvent is volatilized by heating the base material etc. with which the composition was apply | coated. The heating method is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, heating by contact using a hot plate / hot roll, and the like.
Further, heating may be performed in order to fire the resin layer formed by coating or the like.

As the heating temperature (drying and / or firing temperature) in the above case, a suitable temperature can be used according to the type of the solvent and the like. The heating temperature is usually 40 ° C. or higher, preferably 60 ° C. or higher, and more preferably the glass transition temperature or higher of the polyimide resin contained in the heated resin layer.
On the other hand, the heating temperature is usually 400 ° C. or lower, preferably 350 ° C. or lower. When heating temperature is 40 degreeC or more, it is preferable at the point from which a solvent is fully volatilized. In addition, when the heating temperature is 400 ° C. or lower, since the organic solvent does not volatilize rapidly, it is possible to prevent bubbles and the like from being generated in the obtained resin layer. This is preferable because the possibility of reducing the appearance and quality of the resulting resin layer can be reduced. The heating atmosphere may be air or an inert atmosphere, and is not particularly limited. However, when colorless and transparent is required for the resin layer and the polyimide film described later, the atmosphere is inert under nitrogen or the like for color control. It is preferable to heat with.
The glass transition temperature (Tg) of the polyimide resin contained in the heated resin layer of the present invention is not particularly limited, but is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. . Due to the high glass transition temperature, it tends to be applicable to processing steps for various uses.

  The substrate used in the laminate of the present invention is preferably hard and heat resistant. That is, it is preferable to use a material that does not deform under the temperature conditions required in the manufacturing process. Specifically, it is preferable that the base material is made of a material having a glass transition temperature of usually 200 ° C. or higher, preferably 250 ° C. or higher. Specific examples include glass, ceramic, metal, and silicon wafer.

  When glass is used as the substrate, the glass substrate used is not particularly limited. For example, blue plate glass (alkali glass), high silicate glass, soda lime glass, lead glass, aluminoborosilicate glass, Examples include alkali-free glass (borosilicate glass, Corning Eagle XG, etc.), aluminosilicate glass, and the like.

<Polyimide film>
The polyimide film of the present invention can be obtained, for example, by applying the polyimide composition of the present invention to a support as described above and then heating and peeling the resin layer from the support.
The method of peeling the resin layer from the support is not particularly limited, but a method of physically peeling and a method of peeling with a laser are preferable in that the film can be peeled without impairing the performance of the film.

The method of physically peeling is, for example, a method of obtaining a polyimide film by separating the periphery of the laminate including the resin layer / support, a method of obtaining a polyimide film by sucking the periphery, and fixing the support by fixing the periphery. Examples thereof include a method of obtaining a polyimide film by moving it.
In order to use such a physically peeling method, the peeling strength between the support and the resin layer (film) needs to be greater than 0 N / m in the peeling test according to JIS K 6854-2. . If it is 0 N / m, the polyimide film may be displaced or peeled off from the support in the step of forming another layer or the like on the laminate.
In an actual manufacturing process, the laminate may be cut with a laser or a cutter, and then the film may be peeled off. In that case, it is preferable that the film is not peeled until the cut is made, and the peel strength after the cut is preferably a smaller value.
Therefore, the peel strength between the support and the polyimide film is greater than 0 N / m, preferably 0.5 N / m or more, more preferably 1 N / m or more, and usually 1.0 × 10 ³ N / m or less. Furthermore, 7.0 × 10 ² N / m or less is preferable. When the peel strength is in the above range, the film tends not to peel or shift from the support during various steps. Moreover, it exists in the tendency which can peel a support body easily from a laminated body, without damaging a film.

In addition, as a method of evaluating peelability simply, the method of evaluating by the crosscut test according to JISK5400 or 5600 is mentioned.
The thickness of the polyimide film of the present invention is usually 1 μm or more, preferably 2 μm or more, and 300 μm or less, preferably 200 μm or less. When the thickness is 1 μm or more, the polyimide film has sufficient strength and can be obtained as an autonomous film. Therefore, the handling property tends to be improved. Moreover, it exists in the tendency which is easy to ensure the uniformity of a film by making thickness into 300 micrometers or less.

  The linear expansion coefficient of the polyimide film of the present invention is preferably 100 ppm / K or less, more preferably 70 ppm / K or less in the range of 100 to 200 ° C., and more preferably close to the linear expansion coefficient of the substrate. preferable. By being in this range, the deformation of the laminate of the base material and the polyimide tends to be suppressed.

  The transmittance of the polyimide film is not particularly limited and may be colored. However, when colorless and transparent such as device use is required, the transmittance of 500 nm light is usually 70 in a film having a thickness of 1 to 100 μm. % Or more, preferably 80% or more, particularly preferably 85% or more. The transmittance is the total light transmittance at 500 nm according to JIS K 7136-1.

  When the polyimide film is particularly required to be colorless, the yellowness (yellow index (YI)) when the film thickness is 50 ± 5 μm is usually −10 or more, preferably −5 or more, More preferably, it is −1 or more. On the other hand, the upper limit is usually 20 or less, preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less.

  The glass transition temperature (Tg) of the polyimide film of the present invention is not particularly limited, but is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. Due to the high glass transition temperature, it tends to be applicable to processing steps for various uses.

The required performance of the polyimide film depends on the application, but preferably has the following mechanical strength.
The tensile strength of the polyimide film of the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, and is usually 400 MPa or less, preferably 300 MPa or less. The tensile modulus of elasticity is not particularly limited, but is usually 1000 MPa or more, preferably 1500 MPa, and is usually 20 GPa or less, preferably 10 GPa or less.
Further, the tensile elongation is not particularly limited, but is usually 5% GL or more, preferably 10% GL, and is usually 300% GL or less, preferably 200% GL or less.
When the polyimide film has such mechanical strength, it tends to be a film that can withstand various types of processing.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the following examples are shown in order to describe the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

[Synthesis example 1 of polyimide precursor]
Into a 300 mL four-necked flask equipped with a thermocouple, a condenser, and a stirrer was charged 19.2 g of 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-diaminodiphenylsulfone 14 .9 g (0.06 mol), 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride 18.5 g (0.06 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic acid di 17.8 g (0.06 mol) of anhydride and 211 g of N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 8 hours under nitrogen to obtain a polyimide precursor solution 1.

[Synthesis example 2 of polyimide precursor]
4,2′-Diamino-2,2′-bis (trifluoromethyl) biphenyl of Synthesis Example 1 and 4,4′-diaminodiphenyl sulfone were added to 22.0 g (0.11 mol) of 4.4′-diaminodiphenyl ether. 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are converted into 3,3 ′, 4,4′-bicyclohexyltetra A polyimide precursor solution 2 was obtained in the same manner as in Synthesis Example 1 except that 33.4 g (0.11 mol) of carboxylic acid dianhydride was changed to 222 g of N, N-dimethylacetamide.

(Viscosity evaluation)
The viscosity of the polyimide composition was measured at 25 ° C. using a Brooksfield E-type viscometer, and the viscosity before and after the addition of the heterocyclic compound having a hydrogen bonding substituent or an alternative compound thereof was compared.
Before and after the addition, the viscosity did not change or increased, and evaluated as ◯ and decreased as x.

[Create laminate]
The polyimide precursor composition is applied to Corning Eagle XG glass by spin coating so that the film thickness of the polyimide film after drying and baking becomes 10 μm and heated at 330 ° C. or 300 ° C. for 30 minutes. By performing (drying and firing), a polyimide film laminate was obtained.

[Peelability evaluation]
The polyimide film laminate was conditioned overnight at 25 ° C. and 50% humidity, and then peelability was evaluated by a cross-cut method with a cut width of 1 mm.
90 pieces or more peeled off were evaluated as A, 50 pieces or more and less than 90 pieces peeled off as B, 1 piece or more and less than 50 pieces peeled off as C, and those not peeled off evaluated as D. It can be said that the evaluations A and B have good peelability.

[Polarizability]
The average polarizability of the compound used was calculated using chemetch.

[Example 1]
To 6 g of the polyimide precursor solution 1 obtained in the above synthesis example, 1.5 g of NMP and 0.078 g of 4-dimethylaminopyridine were added and stirred to obtain a polyimide composition 1. Viscosity evaluation of the obtained polyimide composition 1 was performed.
Moreover, it apply | coated by the above-mentioned method using the obtained polyimide composition 1, the polyimide laminated body 1 was produced by heating (drying and baking) at 330 degreeC, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 1 was 308 ° C. Moreover, the obtained polyimide film 1 was colorless and transparent.

[Example 2]
A polyimide composition 2 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine in Example 1 was changed to 0.061 g of 4-hydroxypyridine, and the viscosity was evaluated. Moreover, the polyimide laminated body 2 was produced like Example 1, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 2 was 308 ° C. Moreover, the obtained polyimide film 2 was colorless and transparent.

[Example 3]
A polyimide composition 3 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine in Example 1 was changed to 0.061 g of 3-hydroxypyridine, and the viscosity was evaluated. Moreover, it carried out similarly to Example 1, the polyimide laminated body 3 was produced, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 3 was 308 ° C. Moreover, the obtained polyimide film 3 was colorless and transparent.

[Example 4]
Except having changed 4-dimethylamino pyridine of Example 1 into 0.078 g of nicotinamide, it carried out similarly to Example 1, and obtained the polyimide composition 4, and performed viscosity evaluation. Moreover, it carried out similarly to Example 1, the polyimide laminated body 4 was produced, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 4 was 308 ° C. Moreover, the obtained polyimide film 4 was colorless and transparent.

[Example 5]
The polyimide precursor solution 1 of Example 1 was changed to 7.5 g of polyimide precursor solution 2, 4-dimethylaminopyridine was changed to 0.15 g, and NMP was not added. Composition 5 was obtained and evaluated for viscosity. Moreover, it apply | coated like Example 1 and the polyimide laminated body 5 was produced by heating (drying and baking) at 300 degreeC, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 5 was 260 ° C. Moreover, the obtained polyimide film was colorless and transparent.

[Example 6]
The polyimide precursor solution 1 of Example 2 was changed to 7.5 g of polyimide precursor solution 2, 4-hydroxypyridine was changed to 0.13 g, and NMP was not added. Composition 6 was obtained and the viscosity was evaluated. Moreover, it apply | coated like Example 1 and the polyimide laminated body 6 was produced by heating (drying and baking) at 300 degreeC, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 6 was 260 ° C. Moreover, the obtained polyimide film was colorless and transparent.

[Example 7]
The polyimide precursor solution 1 of Example 3 was changed to 7.5 g of polyimide precursor solution 2, 3-hydroxypyridine was changed to 0.13 g, and NMP was not added. Composition 7 was obtained and the viscosity was evaluated. Moreover, it apply | coated like Example 1 and the laminated body 7 was produced by heating (drying and baking) at 300 degreeC, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 7 was 260 ° C. Moreover, the obtained polyimide film was colorless and transparent.

[Comparative Example 1]
A polyimide composition 8 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine in Example 1 was changed to 0.078 g of 4-propylpyridine, and the viscosity was evaluated. Moreover, it carried out similarly to Example 1, the polyimide laminated body 8 was produced, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 8 was 308 ° C.

[Comparative Example 2]
A polyimide composition 9 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine in Example 1 was changed to 0.079 g of 3-aminobenzyl alcohol, and the viscosity was evaluated. Moreover, the polyimide laminated body 9 was produced like Example 1, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 9 was 308 ° C.

[Comparative Example 3]
A polyimide composition 10 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine in Example 1 was changed to 0.051 g of pyridine, and the viscosity was evaluated. Moreover, the polyimide laminated body 10 was produced like Example 1, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 10 was 308 ° C.

[Comparative Example 4]
Except having changed 4-dimethylamino pyridine of Example 1 into 0.051 g of pyrazine, it carried out similarly to Example 1, and obtained the polyimide composition 11, and performed viscosity evaluation. Moreover, the polyimide laminated body 11 was produced like Example 1, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 11 was 308 ° C.

[Comparative Example 5]
A polyimide composition 12 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine in Example 1 was changed to 0.062 g of 1,2-dimethylimidazole, and the viscosity was evaluated. Moreover, the polyimide laminated body 12 was produced like Example 1, and peelability evaluation was performed. The results are shown in Table 1.
The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 12 was 308 ° C.

[Comparative Example 6]
A polyimide composition 13 was obtained in the same manner as in Example 1 except that 4-dimethylaminopyridine of Example 1 was not added. Moreover, it carried out similarly to Example 1, the polyimide laminated body 13 was produced, and peelability evaluation was performed. The results are shown in Table 1. The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 13 was 308 ° C.

[Comparative Example 7]
The polyimide precursor solution 2 was used as the polyimide composition 14, and the polyimide laminated body 14 was produced like Example 1, and peelability evaluation was performed. The results are shown in Table 1. The glass transition temperature of the polyimide resin contained in the resin layer of the polyimide laminate 14 was 260 ° C.

  As shown in Table 1, when the polyimide composition contains a heterocyclic compound having a hydrogen bonding substituent, the peelability is improved, the viscosity is maintained or increased, and the stability of the polyimide composition is good. It has been shown.

  The polyimide composition of the present invention can be used for coating materials, surface protective layers, adhesives, device substrates, insulating films, wiring films and the like.

Claims (10)

  A polyimide composition comprising a polyimide precursor and / or a polyimide and a heterocyclic compound having a hydrogen bonding substituent. 2. The polyimide composition according to claim 1, wherein the heterocyclic compound having a hydrogen bonding substituent has an average polarizability of 60 × 10 ⁻²⁵ cm ³ or more.   The polyimide composition according to claim 1 or 2, wherein the number of heteroelements forming the heterocycle of the heterocyclic compound having a hydrogen bonding substituent is one.   The hydrogen-bonding substituent of the heterocyclic compound which has the said hydrogen-bonding substituent is a substituent which can polarize in a substituent and can form a hydrogen bond between molecules. Polyimide composition.   The polyimide composition as described in any one of Claims 1-4 whose substitution position of the hydrogen bondable substituent of the heterocyclic compound which has the said hydrogen bondable substituent is (beta) position or (gamma) position.     The polyimide composition according to any one of claims 1 to 5, wherein the polyimide precursor and / or polyimide is colorless and transparent.   The polyimide composition according to any one of claims 1 to 6, wherein the polyimide precursor and / or the polyimide has an alicyclic skeleton.   The polyimide laminated body which has a resin layer obtained from the polyimide composition as described in any one of Claims 1-7.   The polyimide film obtained from the polyimide composition as described in any one of Claims 1-7. A step of obtaining a resin layer using a polyimide composition comprising a polyimide precursor and / or a polyimide and a heterocyclic compound having a hydrogen bonding substituent,
Heating the resin layer above the glass transition temperature of the polyimide resin in the resin layer after heating;
The manufacturing method of the polyimide laminated body which has this.