TW202120600A - Polyimide, polyimide resin film, multilayer body and flexible device - Google Patents

Abstract

The present invention provides a polyimide which contains a specific structural unit, and which is characterized in that with respect to the IR spectrum of a resin film formed of this polyimide and having a thickness of 10 [mu]m, if Y is the maximum peak intensity present within the range of from 1,450 to 1,550 cm<SP>-1</SP> and Z is the maximum peak intensity present within the range of from 3,400 to 3,700 cm<SP>-1</SP>, Y and Z satisfy formula 0.1 ≤ Z/Y ≤ 0.4; and this polyimide has good transparency, oxidation resistance and laser releasability from a supporting substrate, while having low in-plane/out-of-plane birefringence, and enables the achievement of a polyimide resin film having excellent flexibility and a flexible device.

Description

Polyimide, polyimide resin film, laminate and flexible device

The invention relates to a polyimide, a polyimide resin film, a laminate and a flexible device.

Compared with glass, organic film has the advantages of flexibility, resistance to cracking, and light weight. Recently, by replacing the substrate of the flat panel display with an organic film, the dynamics of the flexibility of the flat panel display have been activated.

Examples of the resin used in the organic film include polyester, polyamide, polyimide, polycarbonate, polyether sulfide, acrylic, epoxy, cycloolefin polymer, and the like. Among these, polyimide is a highly heat-resistant resin, so it is suitable as a display substrate. However, ordinary polyimide resins are colored brown or yellow due to their high aromatic ring density, so that the transmittance in the visible light region is low, and it is difficult to use them in fields requiring transparency.

In response to the problem of improving the transparency of such polyimide resins, Patent Document 1 discloses that polyimides obtained from alicyclic acid dianhydrides and various aromatic diamines or alicyclic diamines have high transparency. Sex, low birefringence.

In addition, Patent Document 2 discloses a method of obtaining a flexible touch panel using a transparent polyimide resin film obtained by sintering in the air. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-080350 [Patent Document 2] International Publication No. 2018/84067

[The problem to be solved by the invention] However, the polyimide described in Patent Document 1 has the following problem: its resistance to oxidation is low, and when heated in an atmospheric environment, it is easily yellowed due to thermal oxidation. In addition, in the case of fabricating a display on an organic film, a process such as the following is usually: forming an organic film on a supporting substrate, fabricating electronic devices on the organic film, and then peeling off the organic film from the supporting substrate. In this peeling process, the polyimide described in Patent Document 1 has the problems of high irradiation energy required for peeling and poor laser peeling properties.

In addition, Patent Document 2 discloses that a transparent polyimide resin film can be obtained by baking in the air for 30 minutes. However, since the mechanical strength of the transparent polyimide resin film described in Patent Document 2 is slightly low, there is a problem that the polyimide resin film is easily broken during the peeling process as described above. In addition, there is a problem that the bending resistance of the polyimide resin film is small.

The object of the present invention is to provide a polyimide and polyimide resin film that has good transparency, oxidation resistance, laser releasability of a self-supporting substrate, low in-plane/out-of-plane birefringence, and excellent flexibility. [Means to solve the problem]

In order to solve the problem and achieve the object, the present invention is a polyimide comprising a polyimide structural unit A represented by the following formula (1) and a polyimide represented by the following formula (2) The structural unit B and the polyimide structural unit C represented by the following formula (3), and the polyimide is characterized by infrared rays when the polyimide is made into a resin film with a thickness of 10 μm In the (Infrared, IR) spectrum, when ^{the maximum peak intensity in the range of 1450 cm -1} to 1550 cm ^-1 is set to Y, the maximum peak in the range of 3400 cm ^-1 to 3700 cm ^-1 When the intensity is set to Z, the following equation is satisfied. Formula) 0.1≦Z/Y≦0.4

[化1]

(X ¹ represents a direct bond or an oxygen atom; X ² represents an oxygen atom, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -or -Si(CH ₃ ) ₂ -; X ³ represents a direct bond,- SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -) [Effects of the invention]

According to the present invention, it is possible to provide a polyimide and polyimide resin film with good transparency, oxidation resistance, good laser releasability of a self-supporting substrate, low in-plane/out-of-plane birefringence, and excellent flexibility. The polyimide and polyimide resin film of the present invention can be suitably used as flexible devices, such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, color filters, and electronic paper. , Micro-light emitting diode (Light Emitting Diode, LED) displays and other display devices, solar cells, complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) and other light receiving devices, transparent antennas and other communication devices, etc. Substrate. By using such a flexible substrate, a flexible device with high reliability can be manufactured.

Hereinafter, embodiments of the polyimide, polyimide resin film, laminate, and flexible device of the present invention will be described in detail together with the drawings. In addition, the present invention is not limited by the following embodiments.

<Polyimine> The polyimide of the embodiment of the present invention includes a polyimine structural unit A represented by the following formula (1) and a polyimine structural unit represented by the following formula (2) B and the polyimide of the polyimide structural unit C represented by the following formula (3), and when the polyimide is made into a resin film with a thickness of 10 μm, when it will be present in the IR spectrum When the maximum peak intensity in the range of 1480 cm ^-1 to 1510 cm ^-1 is Y, and the maximum peak intensity in the range of 3400 cm ^-1 to 3700 cm ^-1 is Z, the following equation is satisfied.

Formula) 0.1≦Z/Y≦0.4

[化2]

X ¹ represents a direct bond or an oxygen atom. X ² represents an oxygen atom, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -or -Si(CH ₃ ) ₂ -. X ³ represents a direct bond, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -.

In the IR spectrum, it is believed that absorption caused by the skeletal vibration accompanying the carbon-carbon stretching and contraction of the monocyclic aromatic hydrocarbon in the region of ^{1480 cm -1} ～1510 cm ^{-1 appears at 3400 cm -1} ～3700 cm -1 ^{The region of -1} exhibits absorption due to OH stretching with intermolecular hydrogen bonds. Therefore, Z/Y represents the intensity ratio of the peak intensity derived from the intermolecular hydrogen bond to the peak intensity derived from the monocyclic aromatic hydrocarbon.

When Z/Y is less than 0.1, the intermolecular hydrogen bond is weak, so when stress is applied to the polyimide resin film from the outside, it is easy to break. In addition, in the case of greater than 0.4, the intermolecular hydrogen bond is too strong. Therefore, it is considered that when stress is applied to the polyimide resin film from the outside, the stress cannot be relieved inside the film and the film becomes brittle. When Z/Y is 0.1 or more and 0.4 or less, polyimide having good flexibility can be obtained.

The polyimide of the embodiment of the present invention contains, for example, 5 mol% or more and 95 mol% or less of the diamine having a sulfonamide group in all the diamine residues contained in the polyimide, and is used for When the curing conditions for imidization are the heating temperature higher than 230° C. and the heating time is 1 hour or longer, Z/Y is likely to be 0.1 or more and 0.4 or less.

The sulfonyl group has the property of being a hydrogen bond acceptor, and therefore, for example, it forms a hydrogen bond with a hydrogen bond donor such as an amine group or a hydroxyl group present in the polyimide molecule. Therefore, Z becomes larger according to the content of the diamine having a sulfonyl group.

On the other hand, with regard to Y, since the peak intensity is determined by the content of the monocyclic aromatic ring, the maximum peak intensity is roughly determined in a normal aromatic polyimide. Therefore, by adjusting Z, Z/Y can be adjusted to 0.1 or more and 0.4 or less.

In addition, when the curing conditions for the imidization are the above-mentioned conditions, the solvent contained in the polyimide film escapes sufficiently, and the imidization reaction proceeds sufficiently, whereby the polyimide molecules are mutually Packing. From this, it is thought that more hydrogen bonds are formed between the polyimide molecules.

The polyimide of the embodiment of the present invention is excellent in mechanical strength and flexibility by including the polyimine structural unit A, and by including the polyimine structural unit B, it is possible to improve the chemical resistance and reduce the chemical resistance. By increasing the refractive index, by including the polyimide structural unit C, the transparency and laser releasability can be improved without deteriorating the mechanical properties. The polyimide structural unit A is preferably the structural unit A'represented by the following formula (4), and the polyimine structural unit B is preferably the structural unit B'represented by the following formula (5), and the polyimide The imine structural unit C is preferably a structural unit C′ represented by the following formula (6). In formula (4), X ¹ represents a direct bond or an oxygen atom.

[化3]

In addition, polyimide structural unit A, polyimine structural unit B, and polyimine structural unit C are all structures with excellent oxidation resistance. Therefore, even if heated in an atmospheric environment, it is not easy to generate heat caused by thermal oxidation. Caused by yellowing. Therefore, by including all of the polyimide structural unit A, the polyimine structural unit B, and the polyimine structural unit C, transparency, oxidation resistance, and good laser releasability of the self-supporting substrate can be obtained. Polyimide with low in-plane/out-of-plane birefringence and excellent flexibility.

From the viewpoint of further improving the oxidation resistance, the total amount of polyimine structural unit A, polyimine structural unit B, and polyimine structural unit C is preferably 80 moles of all polyimine structural units. Ear% or more, more preferably 90 mole% or more. In addition, the term "all polyimine structural units" refers to all structural units constituting polyimine. When the polyimide contains structural units other than structural unit A, structural unit B, and structural unit C, the total amount (mole basis) of structural unit A, structural unit B, structural unit C and other structural units is all Polyimine structural unit.

In addition, when the ratio (mole basis) of the polyimide structural unit A, the polyimine structural unit B, and the polyimine structural unit C is set as (i): (ii): (iii), Preferably (i): (ii): (iii)=5～80:1～70:1～70, and more preferably (i):(ii):(iii)=10～70:5～60: 5 to 60, particularly preferably (i): (ii): (iii) = 15-60: 15-50: 15-55.

The polyimide of the present invention may contain other structural units within a range that does not hinder the effects of the present invention. Examples of other structural units include polyimine (polyimine containing structural units other than structural unit A, structural unit B, and structural unit C), which is a dehydrated ring-closing body of polyamide acid, and polyhydroxyamide The dehydrated ring-closure polybenzoxazole and so on. As an example of the other structural unit, a polyimide structural unit represented by the general formula (7) (a structural unit other than the structural unit A, the structural unit B, and the structural unit C) can be cited.

[化4]

R ¹ represents a tetravalent tetracarboxylic acid residue, and R ² represents a divalent diamine residue.

Examples of the acid dianhydride used in R ¹ include aromatic acid dianhydrides, alicyclic acid dianhydrides, and aliphatic acid dianhydrides described in International Publication No. 2017/099183. Among them, it is preferable to provide an acid dianhydride having a structure represented by the formula (8) and an acid dianhydride providing a structure represented by the formula (9). When R ¹ includes the structure represented by the general formula (8), a polyimide with a high glass transition temperature can be obtained. In addition, when R ¹ includes the structure represented by the general formula (9), a polyimide having high transparency, low in-plane/out-of-plane birefringence, and a high glass transition temperature can be obtained. These other acid dianhydrides can be used alone or in combination of two or more.

[化5]

Examples of the diamine compound used in R ² include aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds described in International Publication No. 2017/099183. Among them, it is preferable to provide a diamine having a structure represented by any one of formula (10) to formula (15) in terms of compatibility between transparency and heat resistance. These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds can be used alone or in combination of two or more.

[化6]

In addition, the polyimide of the present invention may also contain a triamine skeleton. The triamine has three amine groups, and forms a branched molecular chain by bonding with three tetracarboxylic dianhydride components, so that a polyimide resin film with excellent mechanical strength can be obtained. Such a polyimine precursor having a triamine skeleton can be obtained by using a triamine compound as one of the polymerization components.

Among the specific examples of the triamine compound, as the triamine compound that does not have an aliphatic group, 2,4,4'-triaminodiphenyl ether (2,4,4'-triaminodiphenyl ether, TAPE), 1,3,5-tris(4-aminophenoxy)benzene (1,3,5-tris(4-aminophenoxy)benzene, 1,3,5-TAPOB), 1,2,3-tris(4 -Aminophenoxy)benzene (1,2,3-TAPOB), tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenyl)benzene, 3,4, 4'-triaminodiphenyl ether, etc. In addition, specific examples of triamine compounds having an aliphatic group include tris(2-aminoethyl)amine (TAEA), tris(3-aminopropyl)amine, etc. . Among them, it is preferable to use a component that does not have an aliphatic group and is not easily decomposed by heat. That is, it is preferable to use 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris(4-aminophenoxy)benzene (1,3,5-TAPOB) , 1,2,3-Tris(4-aminophenoxy)benzene (1,2,3-TAPOB), etc.

In addition, the polyimide of the present invention may have a structure represented by the general formula (16) ^{in R 1} and/or R ^2. Since the polyimide has the structure represented by the general formula (16), the residual stress generated between the polyimide resin film obtained by using the polyimide and the supporting substrate can be reduced. Therefore, it is possible to suppress the warpage of the substrate when the polyimide resin film is formed on the supporting substrate.

[化7]

In formula (16), R ³ and R ⁴ each independently represent a monovalent organic group having 1 to 20 carbon atoms. x represents an integer of 3 to 200.

Examples of the monovalent organic group having 1 to 20 carbon atoms in R ³ and R ⁴ include a hydrocarbon group, an amino group, an alkoxy group, and an epoxy group. Examples of the hydrocarbon group in R ³ and R ⁴ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 20 carbons is preferably an alkyl group having 1 to 10 carbons. Specifically, examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and Tributyl, pentyl, hexyl, etc. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include cyclopentyl and cyclohexyl. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the alkoxy group in R ³ and R ⁴ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a phenoxy group, a propyleneoxy group, a cyclohexyloxy group, and the like.

^{R 3} and R ⁴ in the general formula (16) are preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbons or an aromatic group having 6 to 10 carbons. The reason is that the obtained polyimide film has both high heat resistance and low residual stress. Here, the monovalent aliphatic hydrocarbon group having 1 to 3 carbons is preferably a methyl group, and the aromatic group having 6 to 10 carbons is preferably a phenyl group.

X in the general formula (16) is an integer of 3 to 200, preferably 5 to 100, more preferably 5 to 70, and still more preferably an integer of 8 to 50. When x is within the above range, the residual stress of the polyimide can be reduced, and the warpage of the substrate can be reduced. In addition, the polyimide film can be prevented from becoming cloudy or the mechanical strength of the polyimide film is reduced.

The polyimide precursor resin having a structure represented by the general formula (16) can be obtained by using a silicone compound represented by the following general formula (17) as a monomer component.

[化8]

In formula (17), there are a plurality of R ⁵ each independently being a single bond or a divalent organic group having 1 to 20 carbons, and the plurality of R ⁶ , R ⁷ and R ⁸ are each independently having a carbon number of 1 to 20. The monovalent organic group of 20, L ¹ , L ² and L ³ are each independently a group selected from the group consisting of an amino group, an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, a mercapto group, and R ¹⁰ . R ¹⁰ is a monovalent organic group having 1 to 20 carbon atoms. y is an integer of 3 to 200, and z is an integer of 0 to 197.

In the above description, "single key" and "direct key" have the same meaning. That is, it is a state where L ¹ or L ² and Si are directly bonded.

The polyimide of the present invention can be obtained by making a polyimide comprising a structural unit represented by the following formula (18), a structural unit represented by the following formula (19), and a structural unit represented by the following formula (20) The imine precursor is obtained by ring closure of imine.

[化9]

In formulas (18) to (20), Y ¹ to Y ⁶ each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbons, or a monovalent alkylsilyl group having 1 to 10 carbons. R ⁹ represents the tetravalent tetracarboxylic acid residue represented by the formula (21), X ² in the formula (21) represents an oxygen atom, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -or -Si (CH ₃ ) ₂ -. R ¹⁰ represents a divalent diamine residue represented by the formula (22), and X ¹ in the formula (22) represents a direct bond or an oxygen atom. R ¹¹ represents the divalent diamine residue represented by the formula (23), X ³ in the formula (23) represents a straight bond, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -. R ¹² represents a divalent diamine residue represented by formula (24).

[化10]

The method of imidization is not particularly limited, and examples include thermal imidization or chemical imidization. Among them, from the viewpoint of the heat resistance of the polyimide resin film and the transparency in the visible light region, thermal imidization is preferred.

Polyimide precursor resins such as polyamide acid, polyamide acid ester, polyamide silylester, and the like can be synthesized by the reaction of a diamine compound and an acid dianhydride or a derivative thereof. Examples of derivatives include the tetracarboxylic acid of the acid dianhydride, the monoester, diester, triester or tetraester of the tetracarboxylic acid, and the chlorinated acid. Esterified structures such as propyl, n-propyl, isopropyl, n-butyl, second butyl, and tertiary butyl. The reaction method of the polymerization reaction is not particularly limited as long as the target polyimine precursor resin can be produced, and a known reaction method can be used.

As a specific reaction method, the following method can be exemplified: a predetermined amount of all diamine components and solvents are charged in a reactor, and after dissolving them, a predetermined amount of acid dianhydride components are charged at room temperature (25 ℃) ~80℃ Stir for 0.5 hour to 30 hours.

The solvent used is not particularly limited, and a known solvent can be used. For example, as the solvent, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl Isobutylamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, γ-butyrolactone, ethyl lactate, 1,3-Dimethyl-2-imidazolidinone, N,N'-dimethyl propylene urea, 1,1,3,3-tetramethyl urea, dimethyl sulfide, cyclobutane, propylene glycol mono Methyl ether, propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, water, or the solvent described in International Publication No. 2017/099183. These can be used individually or in combination of 2 or more types. Among these, from the viewpoint of the transparency of the obtained polyimide film, γ-butyrolactone is preferred.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 10,000 to 1,000,000, more preferably 30,000 to 500,000, and still more preferably 65,000 to 300,000.

If the weight average molecular weight of the polyimide precursor is within the above range, the strength of the obtained polyimide can be increased without deteriorating the flatness of the obtained coating film.

In addition, the weight average molecular weight, number average molecular weight and molecular weight distribution are based on the DP-8020 Gel Permeation Chromatography (GPC) device manufactured by TOSOH (protection column: TSK guard column ALPHA column) : TSK-GEL α-M, developing solvent: add N,N'-dimethyl acetamide (DMAc), 0.05M-LiCl, 0.05% phosphoric acid) to measure the obtained value.

In order to adjust the molecular weight to a preferable range, the polyimide precursor can also be sealed at both ends with a capping agent. Examples of the blocking agent that reacts with acid dianhydride include monoamines, monohydric alcohols, and the like. In addition, examples of the end-capping agent that reacts with the diamine compound include acid anhydrides, monocarboxylic acids, monochlorine compounds, monoactive ester compounds, dicarbonates, vinyl ethers, and the like. In addition, by reacting the blocking agent, various organic groups can be introduced as terminal groups.

With respect to the acid dianhydride component, the introduction ratio of the sealant at the acid anhydride group terminal is preferably in the range of 0.1 mol% to 60 mol%, and particularly preferably 0.5 mol% to 50 mol%. In addition, with respect to the diamine component, the introduction ratio of the sealant at the amino terminal is preferably in the range of 0.1 mol% to 100 mol%, and particularly preferably 0.5 mol% to 70 mol%. It is also possible to introduce a variety of different end groups by reacting a variety of end-capping agents.

The capping agent introduced into the polyimide precursor can be easily detected by the following method. For example, the polymer into which the capping agent is introduced is dissolved in an acidic solution and decomposed into the amine component and acid anhydride component as the structural unit of the polymer, and the resultant is subjected to gas chromatography (GC) or nuclear magnetic resonance ( Nuclear Magnetic Resonance, NMR) measurement, whereby the blocking agent can be easily detected. In addition, even if it is directly subjected to thermal decomposition gas chromatography (Pyrolysis Gas Chromatography, PGC) or infrared spectroscopy, ¹ H-NMR spectroscopy and ¹³ C-NMR spectroscopy of the polymer into which the capping agent is introduced, it can be easily detected.

There is no particular limitation on the method of producing polyimine by imidizing the polyimide precursor obtained by the method, and a known reaction method can be used. As a specific reaction method, the method of stirring the polyimide precursor solution obtained by the said method at 100-200 degreeC for 0.5 to 30 hours, etc. are mentioned.

＜Polyimide resin composition＞ The polyimide of the embodiment of the present invention is mixed with appropriate components to form a polyimide resin composition. The components that can be contained in the polyimide resin composition are not particularly limited, and examples include solvents, ultraviolet absorbers, thermal crosslinking agents, inorganic fillers, surfactants, internal release agents, colorants, and the like.

(Solvent) The polyimide resin composition of the embodiment of the present invention may contain a solvent. Examples of solvents include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylisobutylamide. Amine, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, γ-butyrolactone, ethyl lactate, 1,3- Dimethyl-2-imidazolidinone, N,N'-dimethyl allylurea, 1,1,3,3-tetramethylurea, dimethyl sulfide, cyclobutane, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, water, or the solvent described in International Publication No. 2017/099183. The solvent contained in the polyimide resin composition of the embodiment of the present invention may be one type or multiple types. Among these, in terms of the transparency of the obtained polyimine and the above-mentioned effects can be obtained by containing a small amount, it is preferable to include γ-butyrolactone, and it is preferable not to include an amide-based solvent. .

(Ultraviolet absorber) The polyimide resin composition of the embodiment of the present invention may contain an ultraviolet absorber. When the polyimide resin composition contains an ultraviolet absorber, it is possible to significantly suppress the deterioration of the transparency or mechanical properties of the polyimide when exposed to sunlight for a long period of time.

As the ultraviolet absorber, a known one can be used without particular limitation. In terms of transparency and non-coloring properties, benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds can be preferably used.

The ultraviolet absorber is preferably a compound having a molecular weight of 1,000 or less. When the ultraviolet absorber is a low-molecular compound with a molecular weight of 1000 or less, the light resistance of the resin film can be improved without increasing the haze of the polyimide resin film.

The content of the ultraviolet absorber in the polyimide resin composition is preferably 0.5 to 5 parts by weight relative to 100 parts by weight of the polyimide resin. When the polyimide resin composition contains an ultraviolet absorber within the above-mentioned range, the light resistance (resistance to light, particularly ultraviolet light) can be improved without impairing the transparency of the resin.

(Thermal crosslinking agent) The polyimide resin composition of the embodiment of the present invention may contain a thermal crosslinking agent. The thermal crosslinking agent is preferably an epoxy compound or a compound having at least two alkoxymethyl groups or hydroxymethyl groups. By having at least two of these groups, the cross-linked structure is formed by the condensation reaction with the resin and the same molecules, and the mechanical strength or chemical resistance of the cured film after the heat treatment can be improved.

The content of the thermal crosslinking agent in the polyimide resin composition is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the polyimide resin. When the polyimide resin composition contains the thermal crosslinking agent within the above range, the mechanical properties and chemical resistance of the resin can be improved without impairing the transparency of the resin.

(Coupling agent) In order to improve the adhesion to the substrate, the polyimide resin composition of the embodiment of the present invention may be added with a coupling agent such as a silane coupling agent and a titanium coupling agent. The content of the coupling agent in the polyimide resin composition is preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the polyimide resin.

(Inorganic filler) The polyimide resin composition of the embodiment of the present invention may contain an inorganic filler. Examples of the inorganic filler include silica microparticles, alumina microparticles, titanium dioxide microparticles, and zirconia microparticles. The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a rod shape, and a fibrous shape.

In order to prevent the scattering of light, the inorganic filler preferably has a small particle size. Specifically, the average particle size of the inorganic filler is preferably 0.5 nm to 100 nm, more preferably 0.5 nm to 30 nm.

The content of the inorganic filler in the polyimide resin composition is preferably 1 part by weight to 100 parts by weight relative to 100 parts by weight of the polyimide resin. When the polyimide resin composition contains an inorganic filler within the above-mentioned range, it is possible to reduce the coefficient of thermal expansion (CTE) or birefringence of the polyimide resin without impairing flexibility.

(Interface active agent) The polyimide resin composition of the embodiment of the present invention may contain a surfactant. When the polyimide resin composition contains a surfactant, the uniformity of the film thickness when the polyimide resin composition is applied can be improved. Examples of surfactants include: FLUORAD (trade name, manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (trade name, manufactured by DIC Co., Ltd.), Salfron (SULFLON) (trade name, manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants. In addition, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), POLYFLOW, and GLANOL (products Name, Kyoeisha Chemical Co., Ltd.), BYK (BYK-Chemie Co., Ltd.) and other organosiloxane surfactants. Furthermore, acrylic polymer surfactants such as POLYFLOW (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be cited.

The content of the surfactant in the polyimide resin composition is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the polyimide resin.

(Internal release agent) The polyimide resin composition of the embodiment of the present invention may contain an internal mold release agent. When the polyimide resin composition contains an internal mold release agent, the releasability of the polyimide resin film from the supporting substrate can be improved. Examples of the internal mold release agent include long-chain fatty acids. The content of the internal mold release agent in the polyimide resin composition is preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the polyimide resin.

(Colorant) The polyimide resin composition of the embodiment of the present invention may contain a coloring agent. By adding a coloring agent to the polyimide resin composition, the color of the polyimide resin film can be adjusted.

As the coloring agent, dyes, organic pigments, inorganic pigments, etc. can be used, but in terms of heat resistance and transparency, organic pigments are preferred. Among them, those having high transparency, light resistance, heat resistance, and chemical resistance are preferred.

＜Polyimide resin film＞ The polyimide resin film of the embodiment of the present invention contains the polyimide. It can be obtained by molding the polyimide or polyimide resin composition into a film shape.

Regarding the polyimide resin film of the embodiment of the present invention, it is preferable to contain 1 ppm or more and 1000 ppm or less of γ-butyrolactone relative to the weight of the polyimide resin film, and it is more preferable to contain 5 ppm or more. , 500 ppm or less of γ-butyrolactone, more preferably 10 ppm or more and 300 ppm or less of γ-butyrolactone. By including γ-butyrolactone in the polyimide resin film at the stated ratio, the mechanical peelability of the self-supporting substrate can be improved without deteriorating the characteristics of the circuits or components formed on the polyimide resin film . In addition, the stress generated at the interface between the polyimide resin film and the circuit or element formed thereon can be alleviated. Therefore, it is possible to improve the crack resistance when a laminate formed by laminating circuits or elements on a polyimide resin film is bent.

As a method of obtaining a polyimide resin film containing 1 ppm or more and 1000 ppm or less of γ-butyrolactone relative to the weight of the polyimide resin film, for example, the following method can be cited: using γ-butyrolactone A polyimide precursor resin solution is prepared as a solvent, and the solution is coated on a supporting substrate, and heated in the range of 240° C. to 290° C. for 45 minutes to 180 minutes to perform thermal imidization.

In addition, the polyimide resin film of the embodiment of the present invention preferably does not contain an amide-based solvent. Since the polyimide resin film does not contain an amide-based solvent, yellowing during thermal imidization can be suppressed and transparency can be improved. As the amide-based solvent preferably not contained, for example, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N ,N-Dimethylisobutylamide, 3-Methoxy-N,N-Dimethylpropionamide, 3-Butoxy-N,N-Dimethylpropionamide, 1,3- Dimethyl-2-imidazolidinone, N,N'-dimethyl allylurea, 1,1,3,3-tetramethylurea, etc.

Furthermore, in the present invention, the content of the solvent contained in the polyimide resin film is the following value: the polyimide resin film cut into long strips is placed in a heating container to be heated, and then removed by heat Gas Chromatograph/Mass Spectrometry (GC/MS) is used to measure the value of the trapped gas. Regarding the polyimide resin film of the embodiment of the present invention, the content of γ-butyrolactone measured by the measurement method is preferably 1 ppm or more and 1000 ppm or less, and the content of the amide-based solvent is preferably Below the detection limit (less than 1 ppm relative to the weight of the polyimide resin film).

The glass transition temperature (Tg) of the polyimide resin film of the embodiment of the present invention is preferably 220°C or higher and 250°C or lower, and more preferably 225°C or higher and 245°C or lower. When the Tg of the polyimide resin film is 220°C or higher, the deformation of the device can be suppressed. In addition, since the Tg of the polyimide resin film is 250°C or less, residual stress can be reduced and warpage can be suppressed. The "warpage" as used herein refers to the degree of curling of the laminate including the film and the supporting substrate as judged by visual observation. The "residual stress" refers to the stress remaining in the film after the resin composition is applied to a substrate such as a glass substrate and the film is formed, and is a reference for "warpage" that may occur in the film. Specifically, it can be measured by the method described in the following Examples.

Hereinafter, the method of manufacturing a polyimide resin film using the polyimide or its composition of embodiment of this invention is demonstrated.

The coating film of the polyimide precursor or the polyimide resin can be formed by coating the resin composition of the polyimide precursor or the polyimide resin composition on the substrate. As a method of coating the polyimide precursor or the resin composition of the polyimide resin on a substrate to form a coating film, include: roll coating method, spin coating method, slit coating method, and use Coating methods such as doctor blades, coaters, etc. Furthermore, in the coating film forming step, the thickness or surface smoothness of the coating film can be controlled by repeated coating. Among them, from the viewpoint of the surface smoothness of the coating film and the uniformity of the film thickness, the slit die coating method is preferred.

The thickness of the coating film can be appropriately selected according to the intended use and is not particularly limited. For example, it is 1 μm to 500 μm, preferably 2 μm to 250 μm, particularly preferably 5 μm to 125 μm. Examples of the substrate include: polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT) ) Film, silicon wafer, glass wafer, oxide wafer, glass substrate, Cu substrate and SUS board, etc. Among them, from the viewpoint of surface smoothness and dimensional stability during heating, a glass substrate is preferred. As the glass constituting the glass substrate, from the viewpoint of dimensional stability, alkali-free glass is particularly preferred.

Then, the solvent is evaporated from the coating film on the substrate, thereby drying the coating film. Specifically, in the drying step, it is sufficient to vacuum or heat dry the coating film. When the transparency of the obtained polyimide resin film is taken into consideration, it is preferable to make the solvent free of cloudiness. evaporation. In the drying of the coating film in the drying step, a hot plate, an oven, an infrared ray, a vacuum chamber, etc. are used.

The heating temperature for drying varies according to the type or purpose of the heated object such as the coating film, and it is preferably performed in the range of room temperature to 170°C for 1 minute to several hours. The room temperature is usually 20°C to 30°C, but preferably 25°C. Furthermore, the drying step may be performed multiple times under the same conditions or under different conditions.

In the case of the polyimide precursor resin, then, a heating step is performed, whereby the polyimide precursor is imidized, thereby forming a polyimide resin film on the substrate. In the case of the polyimide resin, since it has been imidized, the heating step may not be performed. However, by performing the heating step, the mechanical strength or heat resistance of the obtained polyimide resin film can be improved. Therefore, it is preferable to perform a heating step. The environment of the heating step is not particularly limited, and it may be air (oxygen concentration: about 21% by volume), or an inert gas such as nitrogen or argon. Among them, by heating in the atmosphere, a part of the surface of the polyimide resin film is oxidized, and the adhesion between the polyimide resin film and the circuits or components formed on the polyimide resin film is improved, which can improve Since the laminate formed by laminating circuits or components on polyimide has crack resistance when bent, the environment for the heating step is preferably air.

In addition, the time required to reach the heating temperature used in the heating step is not particularly limited, and a heating method according to the heating mode of the manufacturing line can be selected. For example, it is possible to coat the polyimide precursor or polyimide resin formed on the substrate while raising the temperature from room temperature to a heating temperature of 180°C or higher and 550°C or lower in an oven in 5 minutes to 120 minutes. The film is heated. Alternatively, the polyimide precursor or the coating film of the polyimide resin formed on the base material may be directly put into an oven whose temperature has been raised to a range of 180° C. or more and 550° C. or less to be heated. In addition, the coating film of the polyimide precursor or polyimide resin may be heated under reduced pressure if necessary.

In order to obtain the polyimide resin film of the embodiment of the present invention, it is preferable to heat the polyimide precursor or the coating film of the polyimide resin in the range of 240°C or higher and 290°C or lower for 60 minutes or longer. By heating under the above conditions, a polyimide resin film with good transparency and mechanical strength can be obtained.

The polyimide resin film obtained through the above steps may be peeled off from the substrate and used, or may be used as it is without peeling off. As the peeling method, a known method can be used without particular limitation. As an example, a method of immersing in a chemical liquid such as hydrofluoric acid; or a method of irradiating the interface between the polyimide resin film and the substrate with a laser (Laser peeling); or using a single-edged knife to cut the incision at the end and peel it off by lifting it from the end (mechanical peeling), etc. The polyimide resin film of the present invention is excellent in both laser releasability and mechanical releasability. Therefore, it is preferable to perform peeling by either laser peeling or mechanical peeling.

The thickness of the polyimide resin film obtained in the above manner can be appropriately selected according to the intended use, but is preferably 1 μm to 100 μm, more preferably 2 μm to 30 μm, particularly preferably 3 μm to 20 μm.

＜Laminated body＞ The laminate of the embodiment of the present invention includes an insulating layer and/or a wiring layer on the polyimide resin film.

(Insulation) The insulating layer preferably contains an alkali-soluble resin. The alkali solubility in the present invention means that 0.1 g or more is dissolved at 25°C with respect to a 0.045 mass% potassium hydroxide aqueous solution (100 g). The insulating layer formed of an alkali-soluble resin can be patterned by photolithography, thereby forming an opening for conduction of the conductive layer, which is preferable. In addition, the laminate of the embodiment of the present invention preferably has an insulating layer formed of an alkali-soluble resin containing a (meth)acrylic copolymer. The reason is that the (meth)acrylic copolymer in the alkali-soluble resin improves the flexibility of the insulating layer. Furthermore, the film with a conductive layer of the embodiment of the present invention preferably has an insulating layer formed of an alkali-soluble resin containing a cardo-based resin on the conductive layer, and the cardo-based resin has two or more The structure represented by the following structural formula (25). The reason is that the cardo-based resin improves the hydrophobicity of the insulating layer, thereby improving the insulation of the insulating layer.

[化11]

In addition, as the cardo-based resin having two or more structures represented by the structural formula (25), commercially available products can be preferably used. Examples of commercially available products of this cardo-based resin include "WR-301 (trade name)" (manufactured by ADEKA), "V-259ME (trade name)" (Nippon Steel & Sumikin Chemical Co., Ltd.) Manufactured by the company), "OGSOL CR-TR1 (trade name)", "OGSOL CR-TR2 (trade name)", "OGSOL CR-TR3 (trade name) ", "OGSOL CR-TR4 (trade name)", "OGSOL CR-TR5 (trade name)", "OGSOL CR-TR6 (trade name)" ( The above are made by Osaka Gas Chemical (Osaka Gas Chemical), etc.

From the viewpoint of improving coating properties, the weight average molecular weight of the (meth)acrylic copolymer and the cardo resin is preferably 2,000 or more. In addition, from the viewpoint of improving the solubility of the insulating layer in the developer in the pattern formation of the insulating layer, each of these weight average molecular weights is preferably 200,000 or less. Here, the weight average molecular weight refers to a polystyrene conversion value measured by Gel Permeation Chromatography (GPC).

In addition, when the insulating layer contains both a (meth)acrylic copolymer and a cardo-based resin, the weight of the (meth)acrylic copolymer is from the viewpoint of suppressing layer separation and forming a uniform cured film The ratio (Mw(A2)/Mw(A1)) of the average molecular weight (Mw(A1)) to the weight average molecular weight (Mw(A2)) of the cardo-based resin is preferably 0.14 or more. On the other hand, from the viewpoint of suppressing layer separation and forming a uniform cured film, the ratio (Mw(A2)/Mw(A1)) is preferably 1.5 or less, and more preferably 1.0 or less.

The insulating layer in the present invention can be formed using an insulating composition containing an alkali-soluble resin. The content of the alkali-soluble resin contained in the insulating composition can be arbitrarily selected according to the desired film thickness or application, and is usually 10% by mass or more and 70% by mass or less with respect to 100% by mass of the solid content.

The insulating composition may also contain an antioxidant. When the insulating composition contains an antioxidant, the coloration of the insulating layer can be further reduced, and the weather resistance of the insulating layer can be improved. As the type of antioxidant, a compound having a benzotriazole, organic phosphorus, hindered phenol structure, a compound having a hindered amine structure, and the like can be cited. Among these, by containing a compound having a phenolic hydroxyl group and/or a compound having an amine group, the adhesive force between the insulating layer and the base layer is improved, and peeling during bending can be suppressed, which is preferable.

As the compound having a benzotriazole, organophosphorus, and hindered phenol structure, specifically, the compounds described in Japanese Patent Application Laid-Open No. 2019-101440 can be cited, but are not limited to these. Specific examples of the compound having a hindered amine structure include the compounds described in International Publication No. 2015/012228, but are not limited thereto.

Antioxidant can be contained individually or in combination of 2 or more types. The content of the antioxidant in the insulating layer is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the solid content.

The insulating composition may further contain multifunctional monomers, hardeners, ultraviolet absorbers, polymerization inhibitors, adhesion modifiers, solvents, surfactants, dissolution inhibitors, stabilizers, defoamers, and coloring as needed. Agents and other additives.

(Conductive layer) The conductive layer preferably has a mesh structure with a line width of 0.1 μm-9 μm. Since the conductive layer has a mesh structure with a line width of 0.1 μm-9 μm, the conductivity and visibility of the conductive layer can be improved. The line width of the mesh structure of the conductive layer is more preferably 0.5 μm or more, and still more preferably 1 μm or more. On the other hand, the line width of the mesh structure of the conductive layer is more preferably 7 μm or less, and still more preferably 6 μm or less.

In addition, the film thickness of the conductive layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more. On the other hand, the film thickness of the conductive layer is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less.

Examples of the conductive particles contained in the conductive layer include particles described in International Publication No. 2018/084067, and silver particles are more preferable.

In order to form a fine conductive pattern having desired conductivity, the primary particle diameter of the conductive particles is preferably 10 nm to 200 nm, and more preferably 10 nm to 60 nm. Here, the primary particle diameter of the conductive particles is calculated by observing the cross section of the conductive layer with a scanning electron microscope, randomly selecting 100 particles, measuring the primary particle diameter of each particle, and taking the The arithmetic mean of these. In addition, the particle diameter of the primary particle of each particle is taken as the arithmetic mean of the longest part and the shortest part of the primary particles.

From the viewpoint of improving conductivity, the content of conductive particles in the conductive layer is preferably 20% by mass or more, and from the viewpoint of improving pattern processability, it is preferably 95% by mass or less.

In addition, the conductive layer preferably contains 0.1% by mass to 80% by mass of organic compounds. When the conductive layer contains 0.1% by mass or more of an organic compound, flexibility can be imparted to the conductive layer, and the bending resistance of the conductive layer can be further improved. On the other hand, when the conductive layer contains 80% by mass or less of organic compounds, conductivity can be improved.

The organic compound contained in the conductive layer is preferably an alkali-soluble resin. The alkali-soluble resin is preferably a (meth)acrylic copolymer having a carboxyl group. Here, the (meth)acrylic copolymer refers to a copolymer of a (meth)acrylic monomer and other monomers.

As specific examples of (meth)acrylic monomers and other monomers, for example, the examples described in International Publication No. 2018/084067 can be cited, but they are not limited to these.

In order to introduce alkali-soluble carboxyl groups into alkali-soluble resins, for example, (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, these acid anhydrides, etc. may be combined with the (methyl) The method of copolymerization of acrylic monomers.

From the viewpoint of increasing the speed of the curing reaction, the (meth)acrylic copolymer preferably has a carbon-carbon double bond in a side chain or a molecular terminal. As a functional group which has a carbon-carbon double bond, a vinyl group, an allyl group, (meth)acrylic group, etc. are mentioned, for example.

The carboxylic acid equivalent of the alkali-soluble resin is preferably 400 g/mol to 1,000 g/mol. The carboxylic acid equivalent of the alkali-soluble resin can be calculated by measuring the acid value. In addition, in order to achieve a high level of both hardness and crack resistance, the double bond equivalent of the alkali-soluble resin is preferably 150 g/mol to 10,000 g/mol. The double bond equivalent of the alkali-soluble resin can be calculated by measuring the iodine value.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 to 100,000. By setting the weight average molecular weight within the above range, good coating properties of the alkali-soluble resin can be obtained, and the solubility of the alkali-soluble resin in the developer when patterning on the conductive layer also becomes good. Here, the weight average molecular weight of the alkali-soluble resin means a polystyrene conversion value measured by gel permeation chromatography (GPC).

In addition, the conductive layer may contain at least one of an organotin compound and a metal chelate compound. Since the conductive layer contains at least one of an organotin compound and a metal chelate compound, the adhesion between the conductive layer and the gas barrier layer can be further improved. In particular, the metal chelate compound is better than the organotin compound because it can obtain the effect of improving the adhesion without causing an environmental burden. Known compounds can be used for the organotin compound and metal chelate compound.

In addition, the conductive layer may also contain an antioxidant. Since the conductive layer contains an antioxidant, the weather resistance of the conductive layer can be improved. As the type of antioxidant, the same antioxidant as the antioxidant that can be contained in the insulating layer can be cited. Among these, by containing a compound having a phenolic hydroxyl group and/or a compound having an amine group, the adhesive force between the conductive layer and the base layer is improved, and peeling at the time of bending can be suppressed, which is preferable.

Antioxidant can be contained individually or in combination of 2 or more types. The content of the antioxidant in the conductive layer is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the solid content.

The conductive layer preferably contains at least a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermal acid generator, a solvent, a sensitizer, pigments and dyes that absorb under visible light. One is close contact modifiers, surfactants, polymerization inhibitors, antioxidants, etc.

In addition, the conductive layer in the present invention can be formed using a conductive composition. Examples of the components contained in the conductive composition include conductive particles, alkali-soluble resins, organotin compounds, metal chelate compounds, dispersants, photopolymerization initiators, monomers, photoacid generators, Thermal acid generators, solvents, sensitizers, at least one of pigments and dyes that absorb under visible light, adhesion modifiers, surfactants, antioxidants, polymerization inhibitors, and the like.

The conductive particles contained in the conductive composition preferably have a coating layer on at least a part of the particle surface. Thereby, the surface activity of conductive particles can be reduced, and at least one of the reaction between conductive particles and the reaction between conductive particles and organic components can be suppressed, and the dispersibility of conductive particles can be improved. Furthermore, when photolithography is used for the processing of the conductive layer, scattering of exposure light can be suppressed, and the conductive layer can be patterned with high accuracy. On the other hand, the coating layer on the surface of the conductive particles can be easily removed by heating at a high temperature of about 150°C to 350°C in the presence of oxygen. As a result, the conductive particles in the conductive composition can express sufficient conductivity of the conductive layer.

The coating layer on the surface of the conductive particle preferably contains at least one of carbon and a carbon compound. When the coating layer contains at least one of carbon and a carbon compound, the dispersibility of the conductive particles in the conductive composition can be further improved.

As a method of forming a coating layer containing at least one of carbon and a carbon compound on the surface of the conductive particles, for example, a thermal plasma method to make a reactive gas with carbon such as methane gas and conductive particles are used The method of contact (the method described in JP 2007-138287 A), etc.

＜Use＞ The polyimide and polyimide resin film of the embodiment of the present invention can be used as display devices such as liquid crystal displays, organic EL displays, touch panels, electronic paper, color filters, micro LED displays, solar cells, and CMOS Flexible substrates in flexible devices such as light receiving devices, transparent antennas and other communication devices. In particular, the polyimide resin described in this case has excellent oxidation resistance and good transparency, so it can be suitably used for flexible touch panels and flexible solar panels that require high light resistance, reliability and transparency. In various applications of batteries and flexible transparent antennas.

The manufacturing steps of the flexible device include the following steps: forming circuits or components required for the display device and the light receiving device on the polyimide resin film formed on the substrate. For example, a circuit or element required for a device can be formed on a polyimide resin film by a known method. As described above, known methods such as laser peeling or mechanical peeling can be used to peel the solid polyimide resin film on which circuits or elements are formed from the substrate to obtain a flexible device. [Example]

Hereinafter, the present invention will be explained with examples and the like, but the present invention is not limited by these examples.

＜Materials＞ (Acid dianhydride) ODPA: 4,4'-oxydiphthalic dianhydride 6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride PMDA: Pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (Diamine compound) 3,3'-DDS: 3,3'-diaminodiphenyl sulfide BAPS-m: Bis[4-(3-aminophenoxy)phenyl] sulfide TFMB: 2,2'-bis(trifluoromethyl)benzidine 6FODA: 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 4,4'-DDS: 4,4'-diaminodiphenyl sulfide (Triamine compound) TAPOB: 1,3,5-tris(4-aminophenoxy)benzene (Solvent) GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone (Alkali-soluble resin) Alkali-soluble resin (A): Add 0.4 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer containing methacrylic acid/methyl methacrylate/styrene=54/23/23 (mol%) The reaction product (weight average molecular weight (Mw): 29,000) (Conductive particles) A-1: Silver particles (manufactured by Nissin Engineering Co., Ltd.) with an average thickness of the surface carbon coating layer of 1 nm and a primary particle diameter of 40 nm.

＜Evaluation＞ (1) Determination of the weight average molecular weight of the polyimide precursor resin The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) under the following conditions. In addition, the calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by TOSOH Co., Ltd.).

Equipment: DP-8020 (manufactured by TOSOH (stock)) Developing solvent: add N,N'-dimethylacetamide (DMAc), 0.05M-LiCl, 0.05% phosphoric acid Guard column: TSK guard column ALPHA (manufactured by TOSOH (stock)) Column: TSK-GEL α-M (manufactured by TOSOH (stock)) Flow rate: 0.8 mL/min Column temperature: 23℃ Detector: RI-8020 (manufactured by TOSOH (stock)).

(2) Production of polyimide resin film (on glass substrate) Using a spin coater (Mikasa (Mikasa) (stock) "1H-360S (trade name)"), the polyimide precursor resin composition produced in each example and comparative example was cured The film thickness becomes 10 μm±0.5 μm, and it is spin-coated on a 125 mm square and 0.5 mm thick alkali-free glass substrate (AN100, manufactured by AGC), and then used a hot plate (made by Dai Nippon Screen Co., Ltd.) "SCW-636 (trade name)") is pre-baked at 120°C for 5 minutes to make a pre-baked film. The produced substrate was cured under the following conditions to form a polyimide resin film (on a glass substrate).

Example 1 to Example 14, Example 16 to Example 21, Comparative Example 1 to Comparative Example 4: Using an oven ("IHPS-222"; manufactured by ESPEC (stock)), in air The temperature and time described in Table 1 were cured to produce a polyimide resin composition film (on a glass substrate). In addition, curing was performed by putting the substrate into an oven adjusted to the temperature described in each of the Examples and Comparative Examples.

Example 15: Using an inert oven (INH-21CD manufactured by Koyo Thermo System (stock)), the temperature was raised to 250°C for 40 minutes under nitrogen flow (oxygen concentration less than 100 ppm), and kept For 60 minutes, it was cooled to 50°C at 5°C/min-8°C/min to produce a polyimide resin film (on the glass substrate).

The film thickness of the obtained polyimide resin film was measured using a surface roughness/contour shape measuring machine (SURFCOM 1400D; manufactured by Tokyo Precision Co., Ltd.), and the measurement magnification was set to 10,000 times. The length is set to 1.0 mm and the measurement speed is set to 0.30 mm/s to perform the measurement.

(3) Production of polyimide resin film (release film) Use a single-edged knife to cut into the incision at a distance of 1 cm from the four sides of the polyimide resin film (on the glass substrate) made in (2), and peel it off by lifting it from the end. A polyimide resin film (release film) was obtained.

(4) Measurement of IR spectrum peak intensity ratio The IR spectrum peak intensity ratio of the polyimide resin film obtained in (2) was measured by the following method. Analysis method: Fourier Transform Infrared spectroscopy-Attenuated Total Reflection (FTIR-ATR) Device: FTS-55A (manufactured by Bio-Rad) Conditions: ATR accessory (Ge45°) Light source: Special Ceramic detector: MCT Resolution: 4 cm ^-1 Cumulative times: 32 times Measurement range: 400 cm ^-1 ～4000 cm ^-1 Spectral axis: absorbance step 1) ^{Draw with 2000 cm -1} ～4000 cm ^-1 as the reference Step 2) Use the largest peak existing in the range of ^{1480 cm -1} ～1510 cm ^-1 to standardize Step 3) Read the distance between the largest peak ^{existing in the range of 3400 cm -1} ～3700 cm ^{-1 from the baseline} Height step 4) Calculate according to the following formula. Set the maximum peak intensity of the ^{IR spectrum in the range of 1480 cm -1} to 1510 cm ^-1 as Y, which will exist in the range of ^{3400 cm -1} to 3700 cm ^-1 The maximum peak intensity in is set as the peak intensity ratio when Z is the formula) Peak intensity ratio = Z/Y.

(5) Determination of the amount of GBL and NMP contained in the polyimide resin film The amount of GBL contained in the polyimide resin composition is measured by the following procedure. Step 1) Capture of degassing The polyimide resin film (release film) obtained in (3) is cut into long strips and taken into a heating container. Then, the heating container is heated under the following conditions to trap the generated gas in the adsorption tube. A specimen subjected to the same operation without using a sample was used as a control. ·Heating temperature: 400℃ ·Heating time: 60 min ·Environment: Nitrogen 50 mL/min Step 2) Thermal separation from GC/MS Measure the gas trapped in the adsorption tube by the method in step 1 by thermal separation GC/MS. The conditions for thermal separation GC/MS are shown below. ·Thermal release device: TD-100 (Markes) ·One-time thermal release conditions: release temperature 260℃, trap temperature -27℃, 15 min ·Secondary thermal separation conditions: 320℃, 5 min ·GC device: 7890A (Agilent) ·Column: DB-5MS 30 m×0.25 mmID, film thickness 1 μm (Agilent J&W) ·Column temperature: 40℃ (4 min) ~ 280℃ (22 min) heating rate 10℃/min · MS device: 5975C (Agilent) ·Ionization method: Electron ionization (EI) ·Monitoring ion: m/z 29～600 ·GBL quantitative ion: m/z 86 ·NMP quantitative ion: m/z 98 ·Ion source temperature: 230℃ ·Standard products: GBL (Special grade manufactured by Wako Pure Chemical Industries, Ltd.), NMP (Special grade manufactured by Wako Pure Chemical Industries, Ltd.) Use methanol to dissolve the standard to make a standard solution. Take 1 μL from the standard solution prepared by appropriately diluting the solution and inject it into the adsorption tube, and then perform the measurement under the same conditions as the sample to prepare a calibration curve for quantification.

(6) Measurement of glass transition temperature A thermomechanical analysis device (EXSTAR 6000TMA/SS6000 manufactured by SII Nano Technology) was used to measure the glass transition temperature under a nitrogen stream with a tensile load of 30 mN. The heating method is carried out under the following conditions. In the first stage, the temperature was raised to 150°C at a heating rate of 5°C/min and the adsorbed water of the sample of the polyimide resin film was removed, and in the second stage, the temperature was cooled to room temperature with air at a cooling rate of 5°C/min. In the third stage, a formal measurement was performed at a heating rate of 5°C/min, and the glass transition temperature of the sample was determined. In addition, the polyimide resin film (release film) shown in (3) was used in this measurement, the width of the film used in the measurement was set to 5 mm, and the distance between the chucks was set to 20 mm.

(7) Measurement of warpage The glass substrate with the polyimide resin film prepared in (2) was placed on a stone platform, and the amount of warpage after standing for 30 minutes was measured for evaluation. In addition, the amount of warpage is defined as the average value of the floating of the four corners, and the measurement is carried out in a room adjusted to a room temperature of 23°C±2°C and a humidity of 50%±5%.

(8) Determination of yellowness A color meter (SM-T45, manufactured by Suga Testing Machine Co., Ltd.) was used to measure the degree of yellowness. The C light source was used as the light source, and the measurement was performed in transmitted light mode. In addition, the polyimide resin film (on a glass substrate) produced in (2) was used in the measurement; and an oven ("IHPS-222"; manufactured by ESPEC (Stock)) was used to 2) The polyimide resin film (on the glass substrate) prepared in the above is heated at 250°C for 1 hour in the atmosphere (oxygen concentration: 21% by volume). In Table 1, they are expressed as "after curing" and "after additional heating".

(9) Measurement of in-plane/out-of-plane birefringence The TE refractive index (n(TE)) and the TM refractive index (n(TM)) at a wavelength of 632.8 nm were measured using a quince coupler (manufactured by METRICON, PC2010). n(TE) and n(TM) are the refractive indexes in parallel and perpendicular directions with respect to the surface of the polyimide film, respectively. The in-plane/out-of-plane birefringence is calculated as the difference between n(TE) and n(TM) (n(TE)-n(TM)). In addition, the polyimide resin film (release film) obtained in (3) was used for the measurement.

(10) Folding resistance test of polyimide resin film (MIT test) Using the polyimide resin film (release film) obtained in (3), the test was carried out under the following conditions. In addition, it is implemented with the number of measurements as n=3, and the average value thereof is regarded as the number of folding resistance. Test method: According to Japanese Industrial Standards (JIS) P 8115 (2001) Test piece: long strip 110 mm×10 mm Test conditions: Test load: 1.0 kgf Bending angle: 135° R of bending surface: 0.38 mm Bending speed: 175 times per minute Number of measurements: n=3 Test environment: (23±2)℃, (50±5)%RH Measuring device: MIT testing machine model DA (manufactured by Toyo Seiki Co., Ltd.).

(11) Measurement of substrate adhesion (90° peeling test) Cut the polyimide resin film (on the glass substrate) obtained in (2) into 10 mm wide and 100 mm long, and use a hot plate to perform dehydration and baking treatment at 120°C x 6 minutes, and then set it at a stretching speed of 50 A 90° peel test is carried out under the condition of mm/min. Here, in the 90° peel test, the 90° peel strength (N/ cm), and use the following evaluation methods to make judgments. Excellent (A): 0.3 N/cm or less Good (B): 0.3 N/cm or more, less than 0.5 N/cm Pass (C): 0.5 N/cm or more, less than 0.8 N/cm Bad (D): 0.8 N/cm or more.

(12) Laser peel test The polyimide resin film (on the glass substrate) obtained in (2) was irradiated with a 308 nm excimer laser (shape: 21 mm×1.0 mm) from the glass substrate side. Laser peel test. The laser is irradiated while shifting 0.25 mm at a time in the short axis direction. When the incision was made along the edge of the irradiation area, the energy of the peeling film was used as the irradiation energy (peeling energy) required for peeling, and the evaluation was performed using the following criteria. Good (A): The peeling energy is 230 mJ/cm ² or less. Good (B): Irradiation energy exceeds 230 mJ/cm ² , 260 mJ/cm ² or less. Pass (C): Irradiation energy exceeds 260 mJ/cm ² , 300 mJ/cm ² or less. Bad (D): The irradiation energy exceeds 300 mJ/cm ² .

(13) Conductivity evaluation of conductive composition The following method was used to prepare a laminate using the conductive composition and insulating composition prepared in advance, and then the conductivity evaluation using the laminate was performed.

(Production example 1: Production of conductive composition) In Production Example 1, a conductive composition (AE-1) was prepared. Specifically, 80 g of conductive particles (A-1), 4.06 g of surfactant ("DISPERBYK" (registered trademark) 21116: manufactured by DIC Corporation), 98.07 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and 98.07 g of Dipropylene Glycol Methyl Ether (DPM) are mixed, and the homogenizer is used for 30 minutes at 1200 rpm. deal with. Furthermore, the mixture was dispersed using a high-pressure wet type non-medium micronization device nanomizer (manufactured by Nanomizer) to obtain a silver dispersion liquid with a silver content of 40% by mass.

For 20 g of alkali-soluble resin (AR) as an organic compound, 0.6 g of ethyl acetate aluminum diisopropylate as a metal chelate compound (ALCH: manufactured by Kawaken Fine Chemical Co., Ltd.) , 2.4 g of photopolymerization initiator (NCI-831: manufactured by ADEKA) and 12.0 g of PE-3A are mixed, and 132.6 g of PGMEA and 52.6 g of DPM are added and stirred, Thereby, the organic liquid I for the conductive composition is obtained. The silver dispersion liquid and the organic liquid I were mixed at a mass ratio of 72.6/27.4 to obtain a conductive composition (AE-1).

(Production example 2: Production of conductive composition) 0.24 g of Irganox 1010 (manufactured by BASF Japan) as a hindered phenol-based antioxidant was further added to the organic liquid I, and a conductive composition was obtained in the same manner as in Manufacturing Example 1, except that物(AE-2).

(Production example 3: Production of conductive composition) To the organic liquid I was further added 0.24 g of Adekastab LA-87 (manufactured by ADEKA) as a hindered amine-based antioxidant, and it was obtained in the same manner as in Production Example 1 except that Conductive composition (AE-3).

(Production Example 4: Production of conductive composition) To the organic liquid I was further added 0.24 g of Adekastab AO-20 (manufactured by ADEKA) as a hindered phenol-based antioxidant, and the obtained product was obtained in the same manner as in Manufacturing Example 1 except that Conductive composition (AE-4).

(Production Example 5: Production of insulating composition) In Production Example 5, an insulating composition (OA-1) was prepared. Specifically, 50.0 g of Cardo resin (V-259ME: manufactured by Nippon Steel and Sumitomo Chemical Co., Ltd.), 18.0 g of crosslinkable monomer (TAIC: manufactured by Nippon Kasei Co., Ltd.), and 10.0 g of Crosslinkable monomer (M-315: manufactured by Toagosei Co., Ltd.), 20.0 g epoxy compound (PG-100: manufactured by Osaka Gas Chemical Co., Ltd.), 0.2 g photopolymerization initiator (OXE- 01: manufactured by BASF Corporation) and stirred for 1 hour to obtain an insulating composition (OA-1).

(Production Example 6: Production of insulating composition) Except for further adding 0.2 g of Irganox 1010 (manufactured by BASF Japan) as a hindered phenol-based antioxidant, an insulating composition (OA-2) was obtained in the same manner as in Production Example 5.

(Production Example 7: Production of insulating composition) Except for further adding 0.2 g of Adekastab LA-87 (manufactured by ADEKA) as a hindered amine-based antioxidant, an insulating composition (OA- 3).

(Production Example 8: Production of insulating composition) Except for further adding 0.2 g of Adekastab AO-20 (manufactured by ADEKA) as a hindered phenol-based antioxidant, an insulating composition (OA- 4).

(Evaluation of conductivity) Step 1: Formation of insulating layer On the polyimide resin film (on a glass substrate) produced in (2), the insulating composition (OA-1 to OA-4) produced in Production Example 5 to Production Example 8 was applied using a spin coater. ) Spin coating at 1000 rpm for 5 seconds, and then use a hot plate to pre-bake at 100°C for 2 minutes to make a pre-baked film. Using a parallel light mask aligner, use an ultra-high pressure mercury lamp as a light source and expose the prebaked film through a desired mask. Then, using an automatic developing device, it was spray-developed with a 0.045% by mass potassium hydroxide aqueous solution for 60 seconds, and then rinsed with water for 30 seconds to perform pattern processing. The patterned substrate was cured in an oven at 230°C for 60 minutes in air to form an insulating layer with a thickness of 1.0 μm, thereby obtaining a multilayer substrate.

Step 2: Formation of wiring layer Using a spin coater (Mikasa (Mikasa) "1H-360S (trade name)"), under the conditions of 300 rpm for 10 seconds, 500 rpm for 2 seconds, manufacture example 1 to manufacture example 4 The conductive composition (AE-1 to AE-4) prepared in step 1 was spin-coated on the multilayer substrate prepared in step 1, using a hot plate (Dainippon Screen Manufacturing Co., Ltd. "SCW- 636 (trade name)”) The substrate is pre-baked at 100°C for 2 minutes to obtain a pre-baked film with a film thickness of 0.9 μm. Use a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon (Canon) Co., Ltd.), use an ultra-high pressure mercury lamp as a light source, and expose the prebaked film through the desired mask . Then, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), it was spray-developed with a 0.045 mass% potassium hydroxide aqueous solution for 60 seconds, and then rinsed with water for 30 seconds and patterned Processing. Then, using an oven ("IHPS-222"; manufactured by Espec (stock)), post-baking was performed in the air at 230°C for 30 minutes, thereby obtaining a volume resistivity evaluation pattern.

For the obtained volume resistivity evaluation pattern, the surface resistance value ρs (Ω/) was measured by a surface resistance measuring machine ("LORESTA" (registered trademark)-FP; manufactured by Mitsubishi Petrochemical Co., Ltd.) □), measure the film thickness t (cm) with a surface roughness shape measuring machine ("SURFCOM" (registered trademark) 1400D; manufactured by Tokyo Precision Co., Ltd.), multiply the two values, and borrow The volume resistivity (μΩ·cm) was calculated, and the conductivity was evaluated based on the following evaluation criteria. Excellent (A): Less than 60 μΩ·cm Good (B): 60 μΩ·cm or more but less than 80 μΩ·cm Pass (C): 80 μΩ·cm or more, less than 100 μΩ·cm Bad (D): 100 μΩ·cm or more.

(14) Evaluation of bending resistance The same substrate as the substrate produced in (13) was cut into a width of 1 cm, and metal rods with diameters of 1 cm, 5 mm, 1 mm, and 0.8 mm were used to perform a 180-degree bending test. The number of tests was set to 1, and the occurrence of cracks was observed using an optical microscope, and the bending resistance was evaluated based on the following evaluation criteria. Excellent (S): no cracks under 0.8 mm in diameter Excellent (A): no cracks under 1 mm in diameter Good (B): No cracks under 5 mm in diameter, cracks under 1 mm in diameter Pass (C): No cracks under 1 cm in diameter, and cracks under 5 mm in diameter Unqualified (D): Cracks occur under 1 cm in diameter.

Synthesis example 1 Set a thermometer and a stirring rod with stirring wings in a 300 mL four-necked flask. Next, 110 g of GBL was put in under a stream of dry nitrogen, and the temperature was raised to 30°C. After the temperature was raised, 7.00 g (28.2 mmol) of 3,3'-DDS as a diamine compound, 8.87 g (20.5 mmol) of BAPS-m, 0.82 g (2.56 mmol) of TFMB were added while stirring, and 20 g of GBL is cleaned. After confirming that the diamine compound was dissolved, 16.2 g (52.3 mmol) of ODPA as an acid dianhydride was put in, and washed with 20 g of GBL. Then, the temperature was raised to 50°C, and the reaction was carried out for 4 hours. After cooling, 0.02 g of a surfactant (“F-477” manufactured by DIC Co., Ltd.) was added and stirred for 1 hour. The obtained solution was filtered with a polyethylene filter (filter pore size 0.2 μm) to obtain a polyimide precursor resin composition. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 85,000.

Synthesis Example 2 Change 3,3'-DDS to 5.01 g (20.2 mmol), BAPS-m to 8.72 g (20.2 mmol), TFMB to 3.23 g (10.1 mmol), and ODPA to 16.0 g (51.5 mmol) Except for this, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 94,000.

Synthesis Example 3 Change 3,3'-DDS to 5.08 g (20.5 mmol), replace BAPS-m and change to 8.39 g (20.5 mmol) HFBAPP, change TFMB to 3.27 g (10.2 mmol), and change ODPA to 16.2 g ( 52.2 mmol), except for this, in the same manner as in Synthesis Example 1, a polyimide precursor resin composition was obtained. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 97,000.

Synthesis Example 4 Changed 3,3'-DDS to 4.87 g (19.6 mmol), BAPS-m to 8.70 g (20.1 mmol), TFMB to 3.22 g (10.1 mmol), and ODPA to 15.9 g (51.4 mmol) Furthermore, 0.201 g (0.50 mmol) of TAPOB was further added at the same time point as the time when 3,3'-DDS, BAPS-m, and TFMB were added, and except for that, the same procedure as in Synthesis Example 1 was carried out to obtain polyamide Amine precursor resin composition. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 125,000.

Synthesis Example 5 Changed 3,3'-DDS to 4.76 g (19.2 mmol), BAPS-m to 8.29 g (19.2 mmol), TFMB to 3.07 g (9.59 mmol), and ODPA to 11.4 g (36.7 mmol) Furthermore, at the same time point as ODPA, except that 5.43 g (12.2 mmol) of 6FDA was injected, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 92,000.

Synthesis Example 6 Changed 3,3'-DDS to 5.20 g (20.9 mmol), BAPS-m to 9.04 g (20.9 mmol), TFMB to 3.35 g (10.5 mmol), and ODPA to 12.4 g (40.1 mmol) In addition, 2.91 g (13.4 mmol) of PMDA was added at the same time as ODPA, and except for that, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 101,000.

Synthesis Example 7 Changed 3,3'-DDS to 2.45 g (9.87 mmol), BAPS-m to 8.53 g (19.7 mmol), TFMB to 6.32 g (19.7 mmol), and ODPA to 15.6 g (50.4 mmol) Except for this, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 98,000.

Synthesis Example 8 Changed 3,3'-DDS to 2.54 g (10.2 mmol), BAPS-m to 4.41 g (10.2 mmol), TFMB to 9.81 g (30.6 mmol), and ODPA to 16.2 g (52.1 mmol) Except for this, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 102,000.

Synthesis Example 9 A polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 4 except that the solvent used was changed from GBL to NMP. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 120,000.

Synthesis Example 10 3,3'-DDS was changed to 2.50 g (10.1 mmol), BAPS-m was changed to 4.35 g (10.1 mmol), TFMB was changed to 10.15 g (30.2 mmol) of 6FODA, and ODPA was changed to 15.9 g ( 51.3 mmol), except for this, in the same manner as in Synthesis Example 1, a polyimide precursor resin composition was obtained. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 107,000.

Synthesis Example 11 Change 3,3'-DDS to 1.28 g (5.14 mmol), BAPS-m to 2.22 g (5.14 mmol), TFMB to 13.2 g (41.1 mmol), and ODPA to 16.3 g (52.4 mmol) Except for this, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 107,000.

Synthesis Example 12 Changed 3,3'-DDS to 0.64 g (2.58 mmol), BAPS-m to 1.11 g (2.58 mmol), TFMB to 14.9 g (46.4 mmol), and ODPA to 16.3 g (52.6 mmol) Except for this, a polyimide precursor resin composition was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 110,000.

Synthesis Example 13 Changed 3,3'-DDS to 2.55 g (10.3 mmol), BAPS-m to 4.44 g (10.3 mmol), TFMB to 9.88 g (30.8 mmol), and ODPA to 12.2 g (39.3 mmol) Furthermore, 3.86 g (13.1 mmol) of BPDA was added at the same time point as ODPA, and except that it was the same as Synthesis Example 1, a polyimide precursor resin composition was obtained. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 116,000.

Synthesis Example 14 Change 3,3'-DDS to 6.22 g (25.1 mmol), change BAPS-m to 10.8 g (25.1 mmol), change ODPA to 15.9 g (51.2 mmol), and do not use TFMB. In addition, with In Synthesis Example 1, a polyimide precursor resin composition was obtained in the same manner. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 64,000.

Synthesis Example 15 Except having changed 3,3'-DDS to 4,4'-DDS, it carried out similarly to the synthesis example 4, and obtained the polyimide precursor resin composition. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 81,000.

Synthesis Example 16 3,3'-DDS was changed to 5.38 g (21.7 mmol), TFMB was changed to 10.4 g (32.5 mmol), ODPA was changed to 17.1 g (55.3 mmol), and BAPS-m was not used. In Synthesis Example 1, a polyimide precursor resin composition was obtained in the same manner. The weight average molecular weight (Mw) of the polyimide precursor in the obtained composition was 90,000.

Example 1 to Example 21 and Comparative Example 1 to Comparative Example 4 As the polyimide precursor resin composition, the composition described in Table 1 was used, the curing conditions were set as described in Table 1, and the polyimide resin film was produced by the method described in (2) above. The test results of the obtained polyimide resin film are shown in Table 2 below.

[Table 1] Acid dianhydride (mol%) Amine (mol%) Mohr ratio acid dianhydride/amine Solvent Mw Curing conditions ODPA 6FDA PMDA BPDA 3,3'-DDS BAPS-m TFMB 6FODA HFBAPP 4,4'-DDS TAPOB temperature time Oxygen concentration Example 1 Synthesis example 1 100 55 40 5 100/98.0 GBL 85000 250°C 60 min twenty one% Example 2 Synthesis Example 2 100 40 40 20 100/98.0 GBL 94000 250°C 60 min twenty one% Example 3 Synthesis Example 3 100 40 20 40 100/98.0 GBL 97000 250°C 60 min twenty one% Example 4 Synthesis Example 4 100 39 40 20 1 100/98.0 GBL 125000 250°C 60 min twenty one% Example 5 Synthesis Example 5 75 25 40 40 20 100/98.0 GBL 92000 250°C 60 min twenty one% Example 6 Synthesis Example 5 75 25 40 40 20 100/98.0 GBL 92000 250°C 60 min twenty one% Example 7 Synthesis Example 6 75 25 40 40 20 100/98.0 GBL 101000 250°C 60 min twenty one% Example 8 Synthesis Example 7 100 20 40 40 100/98.0 GBL 98000 250°C 60 min twenty one% Example 9 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 250°C 60 min twenty one% Example 10 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 250°C 60 min twenty one% Example 11 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 250°C 60 min twenty one% Example 12 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 250°C 60 min twenty one% Example 13 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 250°C 60 min twenty one% Comparative example 1 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 230°C 30 min twenty one% Example 14 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 300°C 60 min twenty one% Example 15 Synthesis Example 8 100 20 20 60 100/98.0 GBL 102000 250°C 60 min ＜100 ppm Example 16 Synthesis Example 9 100 20 20 60 100/98.0 NMP 120000 250°C 60 min twenty one% Example 17 Synthesis Example 10 100 20 20 60 100/98.0 GBL 107000 250°C 60 min twenty one% Example 18 Synthesis Example 10 100 20 20 60 100/98.0 GBL 107000 250°C 60 min twenty one% Example 19 Synthesis Example 11 100 10 10 80 100/98.0 GBL 107000 250°C 60 min twenty one% Example 20 Synthesis Example 12 100 5 5 90 100/98.0 GBL 110000 250°C 60 min twenty one% Example 21 Synthesis Example 13 75 25 20 20 60 100/98.0 GBL 116000 250°C 60 min twenty one% Comparative example 2 Synthesis Example 14 100 50 50 100/98.0 GBL 64000 250°C 60 min twenty one% Comparative example 3 Synthesis Example 15 100 20 60 20 100/98.0 GBL 81000 250°C 60 min twenty one% Comparative example 4 Synthesis Example 16 100 40 60 100/98 GBL 90000 250°C 60 min twenty one%

[Table 2] Polyimide resin film Touch panel IR peak intensity ratio Z/Y GBL content ppm NMP content ppm Glass transition temperature ℃ Warpage mm Yellowness In-plane/Out-of-plane birefringence MIT test 90° peel strength Laser peelability Conductive composition Insulating composition Conductivity Bending test After curing After additional heating Example 1 0.40 140 - 230 <1 0.9 0.9 0.0014 8000 A A AE-1 OA-1 A B Example 2 0.31 130 - 232 <1 1.0 1.0 0.0016 ＞10000 A A AE-1 OA-1 A A Example 3 0.26 125 - 232 <1 1.2 1.2 0.0015 ＞10000 A A AE-1 OA-1 A A Example 4 0.30 130 - 234 <1 1.0 1.0 0.0016 ＞10000 A A AE-1 OA-1 A A Example 5 0.31 130 - 237 <1 1.2 1.4 0.0016 ＞10000 A A AE-1 OA-1 A A Example 6 0.31 130 - 237 <1 1.2 1.4 0.0016 ＞10000 A A AE-2 OA-2 A S Example 7 0.32 130 - 248 3 2.9 3.4 0.0028 ＞10000 A A AE-1 OA-1 A A Example 8 0.24 115 - 234 <1 1.2 1.2 0.002 ＞10000 A A AE-1 OA-1 A A Example 9 0.21 100 - 236 <1 1.3 1.3 0.0022 ＞10000 A A AE-1 OA-1 A A Example 10 0.21 100 - 236 <1 1.3 1.3 0.0022 ＞10000 A A AE-2 OA-2 A S Example 11 0.21 100 - 236 <1 1.3 1.3 0.0022 ＞10000 A A AE-3 OA-3 A S Example 12 0.21 100 - 236 <1 1.3 1.3 0.0022 ＞10000 A A AE-2 OA-3 A S Example 13 0.21 100 - 236 <1 1.3 1.3 0.0022 ＞10000 A A AE-4 OA-4 A S Comparative example 1 0.04 1500 - 224 <1 1.2 1.2 0.002 4000 A A AE-1 OA-1 C C Example 14 0.22 <1 - 238 <1 1.9 1.9 0.0025 ＞10000 C A AE-1 OA-1 A B Example 15 0.19 110 - 237 <1 1.3 1.3 0.0022 ＞10000 A A AE-1 OA-1 A B Example 16 0.15 - 280 237 <1 2.1 2.1 0.0022 ＞10000 B A AE-1 OA-1 B A Example 17 0.22 110 - 234 <1 1.4 1.4 0.0018 ＞10000 A A AE-1 OA-1 A A Example 18 0.22 110 - 234 <1 1.4 1.4 0.0018 ＞10000 A A AE-2 OA-2 A S Example 19 0.19 85 - 238 <1 1.4 1.4 0.0026 ＞10000 A B AE-1 OA-1 A A Example 20 0.18 75 - 241 <1 1.4 1.4 0.003 ＞10000 A C AE-1 OA-1 A B Example 21 0.22 95 - 244 2 2.2 2.3 0.0051 ＞10000 A A AE-1 OA-1 A A Comparative example 2 0.42 155 - 228 <1 0.8 0.8 0.0014 2800 A - AE-1 OA-1 A C Comparative example 3 0.22 120 - 249 3 1.5 1.5 0.0025 5000 A A AE-1 OA-1 A C Comparative example 4 0.24 120 - 238 <1 1.2 1.2 0.0023 ＞10000 A A AE-1 OA-1 - -

In Examples 1 to 21, good mechanical properties, laser releasability, optical properties, and thermal oxidation resistance were confirmed. In addition, an insulating layer and conductive wiring were formed on the polyimide resin film as an example of a circuit, and the volume resistance and the bending resistance were evaluated. As a result, good characteristics were confirmed.

In Comparative Example 1, since curing did not proceed sufficiently, it is considered that the intermolecular interaction was weak and the mechanical properties were poor. In addition, it is considered that a large amount of GBL remaining in the film acts on the conductive wiring in the curing step to deteriorate conductivity.

In Comparative Example 2, since the structural unit represented by formula (1) is not included, it is considered that the mechanical strength of the obtained polyimide film is reduced. In Comparative Example 3, since 4,4'-DDS was used instead of 3,3'-DDS, it is considered that the yellowness of the obtained polyimide resin film increased and the mechanical strength decreased. In Comparative Example 4, since BAPS-m is not included, it is considered that the chemical resistance of the polyimide film is reduced. In addition, cracks occurred when the insulating composition was applied, so conductivity and bending tests could not be performed.

1: Baseline 2: ^{Maximum peak intensity in the range of 3400 cm -1} to 3700 cm ^-1 3: Maximum peak intensity in the range of 1480 cm ^-1 to 1510 cm ^-1

Fig. 1 is an IR spectrum (2000 cm ^-1 to 4000 cm ^-1 ) of the polyimide resin film of Example 3. Fig. 2 is an IR spectrum (1480 cm ^-1 to 1510 cm ^-1 ) of the polyimide resin film of Example 3. Fig. 3 is an IR spectrum (2000 cm ^-1 to 4000 cm ^-1 ) of the polyimide resin film of Comparative Example 1. Fig. 4 is an IR spectrum (1480 cm ^-1 to 1510 cm ^-1 ) of the polyimide resin film of Comparative Example 1. Fig. 5 is an IR spectrum (2000 cm ^-1 to 4000 cm ^-1 ) of the polyimide resin film of Comparative Example 2. Fig. 6 is an IR spectrum (1480 cm ^-1 to 1510 cm ^-1 ) of the polyimide resin film of Comparative Example 2.

1: Baseline

2: The maximum peak intensity ^{existing in the range of 3400cm -1} ~ 3700cm ^-1

Claims (14)

A polyimide comprising polyimine structural unit A represented by formula (1), polyimine structural unit B represented by formula (2), and polyimine structural unit represented by formula (3) C, and the characteristic of the polyimide is that in the infrared spectrum when the polyimide is made into a resin film with a thickness of 10 μm, it will exist in the range of ^{1480 cm -1} to 1510 cm ^-1 When the maximum peak intensity within is set to Y and the maximum peak intensity existing in ^{the range of 3400 cm -1} to 3700 cm ^-1 is set to Z, the following formula is satisfied; formula) 0.1≦Z/Y≦0.4

(X ¹ represents a direct bond or an oxygen atom; X ² represents an oxygen atom, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -or -Si(CH ₃ ) ₂ -; X ³ represents a direct bond,- SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -). The polyimide according to claim 1, wherein the total amount of the polyimine structural unit A, the polyimine structural unit B, and the polyimine structural unit C is all polyimide More than 80 mole% of the imine structural unit. The polyimide according to claim 1 or 2, wherein the polyimine structural unit A is a structural unit represented by the following formula (4);

(X ¹ represents a direct bond or an oxygen atom). The polyimide according to any one of claims 1 to 3, wherein the polyimine structural unit B is a structural unit represented by the following formula (5);

. The polyimide according to any one of claims 1 to 4, wherein the polyimine structural unit C is a structural unit represented by the following formula (6);

. A polyimide resin film comprising the polyimide according to any one of claim 1 to claim 5. The polyimide resin film according to claim 6, wherein the glass transition temperature is 220°C or higher and 250°C or lower. The polyimide resin film according to claim 6 or 7, wherein γ-butyrolactone is contained in a range of 1 ppm or more and 1000 ppm or less with respect to the weight of the polyimide resin film. The polyimide resin film according to any one of claims 6 to 8, which does not contain an amide-based solvent. A laminated body comprising an insulating layer and/or a conductive layer on the polyimide resin film according to any one of claims 6 to 9. A laminated body comprising an insulating layer and a conductive layer on the polyimide resin film according to any one of claims 6 to 9, and in the laminated body, the insulating layer and the conductive layer Any of them contains antioxidants. The laminate according to claim 11, wherein the antioxidant is a compound containing an amino group or a phenolic hydroxyl group. A flexible device comprising the polyimide resin film according to any one of claims 6 to 9 or the laminate according to any one of claims 10 to 12. The flexible device according to claim 13, wherein the flexible device is a flexible touch panel, a flexible solar cell, or a flexible transparent antenna.

Images