CN104854165A - Resin precursor, resin composition containing same, resin film and method for producing same, laminated body and method for producing same - Google Patents

Abstract

The invention provides a resin precursor, which can obtain a transparent resin cured product without special combination of solvents, and can obtain a resin cured product which has low residual stress generated between the resin cured product and an inorganic film, excellent chemical resistance and small influence of oxygen concentration in a curing process on a YI value and total light transmittance. A resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino-reactive group, the polymerization component containing a polyvalent compound having 2 or more groups selected from the amino group and the amino-reactive group, the polyvalent compound containing a silicon-containing compound, the polyvalent compound containing a diamine represented by the following formula (1), the resin precursor having a structure represented by the following general formula (2), and the amount of the silicon-containing compound being 6 to 25% by mass based on the total mass of the polyvalent compound.

Description

Resin precursor, resin composition containing same, resin film and method for producing same, laminated body and method for producing same

technical field

The present invention relates to a resin precursor, a resin composition containing the same, a resin film and its manufacturing method, and a laminated body and its manufacturing method, which are used, for example, in substrates of flexible devices.

Background technique

In general, for applications requiring high heat resistance, polyimide (PI) resin films are used as resin films. The general polyimide resin is a high heat-resistant resin produced as follows. After solution polymerization of aromatic dianhydride and aromatic diamine, the polyimide precursor is produced, and then ring-closed dehydration and thermal imide are carried out at high temperature. , or chemical imidization using a catalyst.

Polyimide resin is an insoluble and infusible super heat-resistant resin, which has excellent characteristics in thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimide resins are used in a wide range of fields including electronic materials such as insulating coating agents, insulating films, semiconductors, and TFT-LCD electrode protective films. Application in colorless transparent flexible substrates to replace glass substrates used in the field of display materials such as liquid crystal alignment films.

However, general polyimide resins are brown or yellow due to their high aromatic ring density and have low transmittance in the visible light region, making them difficult to use in fields requiring transparency.

Regarding the problem of improving the transparency of such polyimides, for example, Non-Patent Document 1 describes that the transmittance and the transparency of the hue are improved by including an acid dianhydride with a specific structure and a diamine with a specific structure. of polyimide. Furthermore, Patent Documents 1 to 4 describe that by using 4,4-bis(diaminodiphenyl)sulfone (hereinafter also referred to as 4,4-DAS), 3,3-bis(diaminodiphenyl) Base) sulfone (hereinafter, also referred to as 3,3-DAS) and acid dianhydride containing a specific structure, a polyimide with improved transmittance and hue transparency.

In addition, in Examples 9 and 10 of the following Patent Document 6, a polyimide precursor is described in which a specific aromatic tetracarboxylic dianhydride is mixed with an alicyclic diamine or a silicon-containing diamine. Copolymerization can produce polyimide that achieves high Tg, transparency, high adhesion, and low warpage.

Furthermore, in Example 3 of Patent Document 7 and Example 3 of Patent Document 8 below, polyamides obtained by copolymerizing aromatic tetracarboxylic dianhydride, bis(diaminodiphenyl)sulfone, and silicon-containing diamine are described. The imide precursor is used as a resin for semiconductor protection and a photosensitive resin composition.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 61-141732

Patent Document 2: Japanese Patent Application Laid-Open No. 06-271670

Patent Document 3: Japanese Patent Application Laid-Open No. 09-040774

Patent Document 4: Japanese Patent Laid-Open No. 2000-313804

Patent Document 5: International Publication No. 2012/118020 Pamphlet

Patent Document 6: International Publication No. 2011/122198 Pamphlet

Patent Document 7: International Publication No. 1991/010699 Pamphlet

Patent Document 8: Japanese Patent Application Laid-Open No. 4-224823

non-patent literature

Non-Patent Document 1: The Latest Polyimides (Basics and Applications), edited by the Japan Polyimide Research Society, P152

Contents of the invention

The problem to be solved by the invention

However, known transparent polyimides have insufficient physical properties to be used, for example, as semiconductor insulating films, TFT-LCD insulating films, electrode protective films, ITO electrode substrates for touch panels, and heat-resistant colorless and transparent substrates for flexible displays.

For example, when a polyimide resin is used as a colorless and transparent substrate for a flexible display, a polyimide film is formed on a supporting glass (hereinafter also referred to as a support body), and on this polyimide film, usually In other words, in order to fabricate a TFT element, an inorganic film may be formed. When the coefficient of linear expansion (hereinafter also referred to as CTE) of polyimide is high, due to the CTE mismatch between the inorganic film or the supporting glass and the polyimide film, residual material is generated between the polyimide film and the inorganic film. As a result of the stress, there is a problem that the supporting glass is warped and the performance of the TFT element is lowered. Therefore, in order to improve the warpage of the supporting glass, there is a problem of reducing the residual stress of the polyimide. The polyimides described in Patent Documents 1 to 4 have a high residual stress, and when applied to a colorless and transparent substrate for a flexible display, there is a problem that the supporting glass warps.

In addition, in order to produce a polyimide film, it is generally necessary, for example, to coat a polyimide precursor on a glass substrate, and put the glass substrate coated with the polyimide precursor into a drying furnace that introduces nitrogen gas. , heated to 250° C. to 400° C. (hereinafter also referred to as curing step). For polyimides with improved transmittance and hue transparency described in Patent Documents 1 to 4 and Non-Patent Document 1, when the oxygen concentration in the drying furnace during curing is high, specifically, the oxygen concentration is 100 ppm or more In this case, there is a problem that the YI value increases and the total light transmittance decreases, such as oxygen concentration dependence.

Moreover, when using a polyimide resin as a colorless transparent board|substrate for flexible displays, a TFT element is normally produced by the photolithography process using a photoresist on the upper part of a polyimide film. A polyimide film used as a colorless and transparent substrate for a flexible display (hereinafter also referred to as a polyimide substrate) is exposed to the photoresist used in the process of stripping the photoresist included in this process. In chemical agents such as etchant strippers, it is necessary to have chemical resistance to these chemicals. For the polyimide formed of 4,4-DAS, 3,3-DAS and acid dianhydride containing a specific structure as described in Patent Document 1, during the photoresist stripping process, due to the polyimide There is a problem in terms of chemical resistance, such as the occurrence of microscopic cracks in the imide substrate, the phenomenon that the polyimide substrate becomes cloudy, and the total light transmittance decreases.

Patent Document 5 describes introducing a soft silicon-containing diamine by block copolymerization for the purpose of maintaining the glass transition temperature and Young's modulus of polyimide and reducing residual stress. However, as described in Comparative Example 4 of Patent Document 5, when a silicon-containing diamine is block-copolymerized, unless a special combination of solvents is used to dissolve the polyimide precursor, the silicone moiety occurs. The phases are separated, and the structure of the island portion in the sea-island structure having different refractive indices becomes larger, so that the film becomes cloudy and the total light transmittance decreases. In addition, when using a combination of special solvents with a low boiling point, when the polyimide precursor solution is applied to the substrate and left at room temperature for several hours, turbidity and white turbidity of the coating film may occur, and it is necessary to control the standing time . In this way, when making a transparent thermosetting film from polyimide with silicon-containing diamine block copolymerized, it is necessary to use a special combination of solvents to dissolve the precursor, and in addition, it is necessary to control the standing time after coating the precursor solution .

In addition, Examples 9 and 10 of Patent Document 6 describe polyimide precursors obtained by copolymerizing aromatic tetracarboxylic dianhydrides, alicyclic diamines, and silicone diamines, and polyimide precursors obtained therefrom. Polyimide. However, after the present inventors have confirmed, they have found that the polyamide has a high yellowness index, low total light transmittance, and the problem that the yellowness index and transmittance are easily affected by the oxygen concentration when the polyimide is cured (refer to this application Specification comparative example 25).

In addition, Patent Documents 7 and 8 describe polyimide precursors obtained by copolymerizing (diaminodiphenyl) sulfone, aromatic tetracarboxylic dianhydride, and silicone diamine, and polyimide precursors obtained therefrom. Polyimide. However, after confirmation by the present inventors, it was found that there was the following problem: the silicon-containing The mass ratio of the monomer of the base is less in Patent Document 7, so the residual stress of the obtained polyimide is large, which is not suitable for display technology; on the other hand, it is more in Patent Document 8, Therefore, the obtained polyimide becomes cloudy and is unsuitable for use in a transparent display (see Comparative Examples 23 and 24 in the specification of this application).

The present invention has been made in view of the problems described above, and aims to provide a resin precursor capable of obtaining a transparent cured resin without a special combination of solvents and capable of obtaining an interfacial bond with an inorganic film. Cured resin with low residual stress, excellent chemical resistance, and little influence of oxygen concentration during the curing process on YI value and total light transmittance. Another object of the present invention is to provide a resin composition containing the resin precursor, a resin film cured from the resin composition, a method for producing the same, a laminate, and a method for producing the same.

solutions to problems

In order to solve the above problems, the inventors of the present invention conducted intensive studies and found that a heat-resistant resin precursor with a specific structure can form a transparent cured resin without a combination of special solvents. The present invention was completed based on the knowledge that the residual stress generated between the resins is low, the chemical resistance is excellent, and the influence of the oxygen concentration during the curing process on the YI value and the total light transmittance is small. That is, the present invention is as follows.

[1] The resin precursor, which is a resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino-reactive group,

The polymeric component comprises a polyvalent compound having two or more groups selected from amino groups and amino-reactive groups,

The polyvalent compound comprises a silicon-containing compound,

The polyvalent compound contains a diamine represented by the following formula (1),

The resin precursor has a structure represented by the following general formula (2),

{In formula (2), a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200. },

The amount of the silicon group-containing compound is 6 mass % to 25 mass % based on the total mass of the polyvalent compound.

[2] The resin precursor according to [1], wherein the amino-reactive group contains one or more types selected from the group consisting of carboxyl groups, substituted carboxyl groups, and acid anhydride groups.

[3] The resin precursor according to [1] or [2], wherein the silicon group-containing compound contains an organosilicon compound represented by the following general formula (3):

{In formula (3), there are a plurality of R ₂ each independently being a single bond or a divalent organic group with 1 to 20 carbons, R ₃ and R ₄ each independently being a monovalent organic group with 1 to 20 carbons Groups, there may be multiple R ₅ each independently a monovalent organic group with 1 to 20 carbon atoms, L ₁ , L ₂ and L ₃ each independently an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group group, acid halide group, hydroxyl group, epoxy group, or mercapto group, j is an integer of 3-200, and k is an integer of 0-197. }.

[4] The resin precursor according to [3], wherein, in the general formula (3), L ₁ and L ₂ are each independently an amino group or an acid anhydride group, and k is 0.

[5] The resin precursor according to [4], wherein, in the general formula (3), L ₁ and L ₂ are both amino groups.

[6] The resin precursor according to any one of [1] to [5], wherein the resin precursor contains unit 1 and unit 2,

The unit 1 has at least a structure represented by the following general formula (4):

{In the formula (4), there are a plurality of R ₁ each independently being a hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and there may be a plurality of X ₁ each independently being A tetravalent organic group having 4 to 32 carbon atoms, and n is an integer of 1 to 100. },

This unit 2 has the structure represented by the following general formula (5) or the structure represented by the following general formula (6), or has the structure represented by the general formula (5) and the structure represented by the general formula (6) Structure both,

{In formula (5), there are multiple R ₁ each independently hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and multiple R ₂ are each independently carbon A divalent aliphatic hydrocarbon with a number of ₃ to 20, or a divalent aromatic group, _R3 and R4 are each independently a monovalent organic group with a carbon number of 1 to ₂₀ , and there may be a plurality of X2 each independently A tetravalent organic group having 4 to 32 carbon atoms, l is an integer of 3 to 50, and m is an integer of 1 to 100. },

{In formula (6), there are a plurality of R ₁ each independently hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and a plurality of R ₃ and R ₄ are each independently It is a monovalent organic group with 1 to 20 carbons, and there are a plurality of R ₈ each independently being a trivalent aliphatic hydrocarbon with 3 to 20 carbons, or a trivalent aromatic group, and p is 1 to 100 Integer, and q is an integer of 3-50. }.

[7] The resin precursor according to [6], wherein the total amount of the unit 1 and the unit 2 is 30% by mass or more based on the total mass of the resin precursor.

[8] The resin precursor according to [6] or [7], further comprising a unit 3 having a structure represented by the following general formula (7):

{In the formula (7), there are a plurality of R ₁ each independently hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and there may be a plurality of X ₃ each independently A divalent organic group having 4 to 32 carbons may exist in plural. X ₄ is each independently a tetravalent organic group having 4 to 32 carbons, and t is an integer of 1 to 100. }.

[9] The resin precursor according to [8], wherein, in the general formula (7), X ₃ is a residue having the structure of 2,2'-bis(trifluoromethyl)benzidine from which the amino group has been removed. base.

[10] The resin precursor according to any one of [6] to [9], wherein the unit 1 and the unit 2 are based on the total amount of acid dianhydride sites derived from the unit 1 and the unit 2 The amount calculated as 60 mol% or more contains one or more moieties derived from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) and derived from the group selected from 4,4 '-Oxodiphthalic dianhydride (ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), cyclohexane-1,2,4,5- Tetracarboxylic dianhydride (CHDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis(trimellitic acid monoester anhydride) ( TAHQ) and 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF) in combination of one or more sites.

[11] The resin precursor according to any one of [1] to [10], wherein the R ₃ and the R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a carbon number 6-10 monovalent aromatic hydrocarbon groups.

[12] The resin precursor according to any one of [1] to [11], wherein at least a part of the R ₃ and the R ₄ are phenyl groups.

[13] The resin precursor according to any one of [1] to [12], wherein the resin obtained by heating and curing the resin precursor at 300 to 500° C. in an inert atmosphere is - The range of 150°C to 0°C has at least one glass transition temperature and the range of 150°C to 380°C has at least one glass transition temperature, and the range of greater than 0°C and less than 150°C has no glass transition temperature.

[14] The resin precursor according to any one of [1] to [13], which contains 20 mol% or more of the acid dianhydride moieties derived from the resin precursor based on the total amount of acid dianhydride sites derived from The site of pyromellitic dianhydride (BPDA).

[15] The resin precursor according to any one of [1] to [14], wherein a part of the resin precursor is imidized.

[16] A precursor mixture comprising the resin precursor described in any one of [1] to [15] and a resin precursor having a structure represented by the following general formula (8),

{In the formula, there may be a plurality of X ₃ each independently being a tetravalent organic group with 4 to 32 carbons, and a plurality of R ₁ each independently being a hydrogen atom, a monovalent aliphatic group with 1 to 20 carbons hydrocarbon, or a monovalent aromatic group, and r is an integer of 1-100. }.

[17] A flexible device material comprising the resin precursor described in any one of [1] to [15] or the precursor mixture described in [16].

[18] A resin film which is a cured product of the resin precursor described in any one of [1] to [15] or a cured product of the precursor mixture described in [16].

[19] A resin composition comprising the resin precursor according to any one of [1] to [15] or the precursor mixture according to [16], and a solvent.

[20] The resin composition according to [19], wherein the resin obtained by developing the resin composition on the surface of the support has a yellowness index of 7 or less at a film thickness of 20 μm, It is obtained by imidating the said resin precursor contained in this resin composition by heating this resin composition at 300-500 degreeC in nitrogen atmosphere.

[21] The resin composition according to [19] or [20], wherein the resin obtained by spreading the resin on the surface of the support exhibits a residual stress of 25 MPa or less at a film thickness of 10 μm After the composition, the resin precursor contained in the resin composition is imidized by heating the resin composition at 300° C. to 500° C. in a nitrogen atmosphere.

[22] A resin film which is a cured product of the resin composition according to any one of [19] to [21].

[23] A method of manufacturing a resin film, comprising:

A step of spreading the resin composition according to any one of [19] to [21] on the surface of the support;

heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film; and

A step of peeling the resin film from the support.

[24] A laminate comprising a support and a resin film formed on the surface of the support, the resin film being cured resin composition according to any one of [19] to [21]. things.

[25] A method of manufacturing a laminate comprising:

A step of spreading the resin composition described in any one of [19] to [21] on the surface of the support; and

A step of heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film, thereby obtaining a laminate including the support and the resin film.

[26] A polyimide resin film used in the manufacture of a display substrate, having an Rth of 20 to 90 nm at a thickness of 20 μm.

[27] A manufacturing method of a display substrate, comprising:

A step of spreading a resin composition comprising a polyimide precursor on the surface of the support;

A step of heating the support and the resin composition to imidize the polyimide precursor to form the polyimide resin film described in [26];

A process of forming an element on the polyimide resin film; and

A step of peeling the polyimide resin film forming the element from the support.

The effect of the invention

According to the present invention, it is possible to provide a resin precursor, which can obtain a transparent cured resin without a combination of special solvents, and can obtain a low residual stress generated between the inorganic film and an excellent chemical resistance, and can be obtained during the curing process. Cured resin with little effect of oxygen concentration on YI value and total light transmittance.

Detailed ways

Hereinafter, exemplary embodiments of the present invention (hereinafter, simply referred to as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, Various deformation|transformation can be implemented within the range of the summary. It should be noted that the number of repetitions of the structural unit in the formula of the present disclosure is only the number of the structural unit that can be included in the entire resin precursor unless otherwise specified, and therefore, it should be noted that it does not refer to a specific structure such as a block structure. Bonding method. In addition, unless otherwise specified, the characteristic values described in the present disclosure refer to values measured by the method described in the item of [Examples] or a method equivalent thereto that can be understood by those skilled in the art.

<Resin precursor>

A resin precursor is provided. The resin precursor according to the embodiment of the present invention is a resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino reactive group,

The polymeric component comprises a polyvalent compound having two or more groups selected from amino groups and amino-reactive groups,

The multivalent compound comprises a silicon-containing compound,

The polyvalent compound contains a diamine represented by the following formula (1),

The resin precursor has a structure represented by the following general formula (2),

{In formula (2), a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200. },

The amount of the silicon group-containing compound is 6 mass % to 25 mass % based on the total mass of the polyvalent compound.

The polymeric component contains amino groups and amino-reactive groups. The polymeric component comprises a polyvalent compound having two or more groups selected from amino groups and amino-reactive groups. For example, the polymeric component may be a mixture of a polyvalent compound having an amino group and a polyvalent compound having an amino-reactive group, or may be a polyvalent compound containing both an amino group and an amino-reactive group, or may be a combination thereof.

In the present disclosure, an amino-reactive group refers to a group that is reactive toward an amino group. Examples of amino-reactive groups include acid groups (such as carboxyl groups, acid anhydride groups, and substituted carboxyl groups (such as ester groups, acid halide groups, etc.), hydroxyl groups, epoxy groups, and mercapto groups. As a compound containing an acidic group, dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, and the acid dianhydride of these carboxylic acids, an ester compound, acid chloride, etc. are mentioned, for example. Therefore, the resin precursor of this embodiment may be a polyimide precursor. In a typical embodiment, the amino-reactive group contains one or more types selected from the group consisting of carboxyl groups, substituted carboxyl groups, and acid anhydride groups. In a preferred embodiment, the amino-reactive group is one or more types selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group.

The polyvalent compound contains at least diamine represented by the general formula (1). The compound represented by the general formula (1) can be selected from, for example, 4,4-(diaminodiphenyl)sulfone (hereinafter also referred to as 4,4-DAS), 3,4-(diaminodiphenyl) One or more of the group consisting of sulfone (hereinafter also referred to as 3,4-DAS) and 3,3-(diaminodiphenyl)sulfone (hereinafter also referred to as 3,3-DAS).

At least one of the polyvalent compounds is a silicon group-containing compound. The structure represented by the general formula (2) is derived from a silicon group-containing compound. The amount of the silicon group-containing compound is 6% by mass to 25% by mass based on the mass of the polyvalent compound (hereinafter, this mass fraction is also referred to as the concentration of the silicon group-containing monomer). The concentration of the silicon group-containing monomer is 6% by mass or more from the viewpoint of sufficiently obtaining the effect of reducing the stress generated between the resin film and the inorganic film and the effect of reducing the yellowness index, and it is preferably 7% by mass or more. More preferably, it is 8 mass % or more, More preferably, it is 10 mass % or more. On the other hand, the silicon group-containing monomer concentration of 25% by mass or less is advantageous from the viewpoint of obtaining a polyimide that does not become cloudy, improves transparency, reduces the yellowness index, and obtains good heat resistance. Preferably it is 22 mass % or less, More preferably, it is 20 mass % or less. From the standpoint of making chemical resistance, YI value, total light transmittance, birefringence, residual stress, and oxygen dependence of optical properties good, the concentration of the silicon group-containing monomer is particularly preferably 10% by mass or more and 20% by mass or less.

In the general formula (2), a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbons include monovalent hydrocarbon groups having 1 to 20 carbons, amino groups having 1 to 20 carbons, alkoxy groups having 1 to 20 carbons, and epoxy groups.

Examples of the monovalent hydrocarbon group having 1 to 20 carbons include an alkyl group having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons, an aryl group having 6 to 20 carbons, and the like. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, and specific examples include methyl, ethyl, propyl, and isopropyl. Base, butyl, isobutyl, tert-butyl, pentyl, hexyl, etc. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms from the above viewpoint, 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 from the above viewpoint, and specific examples include phenyl, tolyl, naphthyl and the like.

Examples of the amino group having 1 to 20 carbon atoms include an amino group, a substituted amino group (for example, bis(trialkylsilyl)amino group), and the like.

Examples of the monovalent alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, propyleneoxy and cyclohexyloxy. wait.

In the general formula (2), from the viewpoint of obtaining both high heat resistance and low residual stress in the obtained polyimide film, it is preferable that a plurality of _R3 and R4 are each independently monovalent with 1 to ₃ carbon atoms. An aliphatic hydrocarbon group, or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms. From this point of view, the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group, and the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

h in the general formula (2) is an integer of 3-200, preferably an integer of 10-200, more preferably an integer of 20-150, still more preferably an integer of 30-100, particularly preferably an integer of 35-80. When h is 2 or less, the residual stress of the polyimide obtained from the resin precursor of the present disclosure sometimes deteriorates (i.e., becomes larger), and when h exceeds 200, when a varnish containing a resin precursor and a solvent is prepared, the varnish whiteness sometimes occurs. problems such as turbidity and reduction in the mechanical strength of polyimide.

In the resin precursor of the present embodiment, the silicon-containing compound preferably includes an organosilicon compound represented by the following general formula (3):

{In the formula, there are multiple R ₂ each independently a single bond or a divalent organic group with 1 to 20 carbons, R ₃ and R ₄ each independently a monovalent organic group with 1 to 20 carbons, There may be a plurality of R ₅ each independently being a monovalent organic group with 1 to 20 carbon atoms, L ₁ , L ₂ and L ₃ each independently being an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an ester group, an acyl group Halo, hydroxyl, epoxy, or mercapto, j is an integer of 3-200, and k is an integer of 0-197. }. In a preferred embodiment, the silicon group-containing compound is an organosilicon compound represented by the general formula (3).

Examples of the divalent organic group having 1 to 20 carbons in R2 include methylene, an alkylene group having ₂ to 20 carbons, a cycloalkylene group having 3 to 20 carbons, and a cycloalkylene group having 6 to 20 carbons. The arylene group and so on. The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance, residual stress, and cost, and examples include dimethylene, trimethylene, and tetramethylene. Methyl, pentamethylene, hexamethylene, etc. The cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms from the above viewpoint, and examples thereof include cyclobutylene group, cyclopentylene group, cyclohexylene group, and cycloheptylene group. wait. Among them, divalent aliphatic hydrocarbons having 3 to 20 carbon atoms are preferable from the above viewpoint. The arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms from the above viewpoint, and examples thereof include phenylene and naphthylene.

In general formula (3), R ₃ and R ₄ are synonymous with R ₃ and R ₄ in general formula (2), and the preferred mode is as described above for general formula (2). In addition, R ₅ is a monovalent organic group with 1 to 20 carbons, that is, it is synonymous with R ₃ and R ₄ , and the preferred mode is the same as R ₃ and R ₄ .

In the general formula (3), L ₁ , L ₂ and L ₃ are each independently an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an ester group, an acid halide group, a hydroxyl group, an epoxy group, or a mercapto group.

The amino group may be substituted, for example, bis(trialkylsilyl)amino group etc. are mentioned. Specific examples of compounds represented by the general formula (3) in which L ₁ , L ₂ and L ₃ are amino groups include amino-modified methyl phenyl silicones at both ends (for example, Shin-Etsu Chemical Co., Ltd. X22-1660B-3 (number average molecular weight 4,400) and X22-9409 (number average molecular weight 1,300)), two-terminal amino-modified dimethyl silicone (such as X22- 161A (number average molecular weight 1,600), X22-161B (number average molecular weight 3,000) and KF8012 (number average molecular weight 4,400); BY16-835U (number average molecular weight 900) manufactured by Dow Corning Toray Co., Ltd.; and CHISSO CORPORATION SilaplaneFM3311 (number average molecular weight 1000)) and so on.

Specific examples of compounds in which L ₁ , L ₂ , and L ₃ are isocyanate groups include isocyanate-modified silicones obtained by reacting the aforementioned both-terminal amino-modified silicone and a phosgene compound.

Specific examples of compounds in which L ₁ , L ₂ , and L ₃ are carboxyl groups include X22-162C (number average molecular weight: 4,600) manufactured by Shin-Etsu Chemical Co., Ltd., and X22-162C manufactured by Dow Corning Toray Co., Ltd. BY16-880 (number average molecular weight 6,600) and so on.

Specific examples of compounds in which L ₁ , L ₂ , and L ₃ are acid anhydride groups include acyl compounds having at least one of groups represented by the following formula groups.

Specific examples of compounds in which L ₁ , L ₂ and L ₃ are acid anhydride groups include X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-168A (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000), X22-168B (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), X22-168-P5-8 (Shin-Etsu Chemical Co., Ltd. ., number average molecular weight 4,200), DMS-Z21 (manufactured by IPROS CORPORATION, number average molecular weight 600 to 800), etc.

Specific examples of the compounds in which L ₁ , L ₂ and L ₃ are ester groups include compounds obtained by reacting the aforementioned compounds in which L ₁ , L ₂ and L ₃ are carboxyl or acid anhydride groups and alcohols.

Specific examples of compounds in which L ₁ , L ₂ , and L ₃ are acid halide groups include carboxylic acid chlorides, carboxylic acid fluorides, carboxylic acid bromides, and carboxylic acid iodides.

Specific examples of compounds in which L ₁ , L ₂ and L ₃ are hydroxyl groups include KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), KF-6001 (manufactured by Shin-Etsu Chemical Co. , Ltd., number average molecular weight 1,800), KF-6002 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), KF-6003 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,000), etc. It is believed that a compound having a hydroxyl group reacts with a compound having a carboxyl group or an anhydride group.

Specific examples of compounds in which L ₁ , L ₂ , and L ₃ are epoxy groups include X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 400), which is epoxy-type at both ends, KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 980), X22-163A (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000), X22-163B (manufactured by Shin-Etsu Chemical Co. ., Ltd., number average molecular weight 3,500), X22-163C (Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,400); X22-169AS (Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-169B (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400); X22-9002 (Shin- Etsu Chemical Co., Ltd. product, functional group equivalent weight 5,000 g/mol) and the like. It is believed that compounds having epoxy groups react with diamines.

Specific examples of compounds in which L ₁ , L ₂ and L ₃ are mercapto groups include X22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400), X22-167C (manufactured by Shin-Etsu Chemical Co. ., Ltd., number average molecular weight 4,600), etc. It is believed that compounds having mercapto groups react with compounds having carboxyl or anhydride groups.

From the viewpoint of increasing the molecular weight of the resin precursor, or from the viewpoint of the heat resistance of the obtained polyimide, it is preferable that L ₁ , L ₂ and L ₃ are each independently an amino group or an acid anhydride group, and further avoiding the inclusion of the resin before From the viewpoint of white turbidity of the varnish of the body and the solvent, or from the viewpoint of cost, it is more preferable that each independently be an amino group.

Either from the viewpoint of avoiding cloudiness of the varnish containing the resin precursor and the solvent, or from the viewpoint of cost, it is preferable that L1 and L2 are each independently _an amino group or an _acid anhydride group, and k is 0. _In this case, it is more preferable that L1 and L2 are _both amino groups.

In the general formula (3), the preferred mode of j is the same as the description about h in the previous general formula (2). In general formula (3), k is an integer of 0-197, Preferably it is 0-100, More preferably, it is 0-50, Especially preferably, it is 0-25. When k exceeds 197, problems such as white turbidity of the varnish may arise when preparing a varnish containing a resin precursor and a solvent. It is preferable that k is 0 from a viewpoint of increasing the molecular weight of a resin precursor, or from a viewpoint of the heat resistance of the obtained polyimide. When k is 0, it is advantageous that j is 3-200 from the viewpoint of increasing the molecular weight of the resin precursor or the heat resistant viewpoint of the obtained polyimide.

In a preferred form, from the perspective of residual stress and cost, _R3 and R4 in the various formulas of the present disclosure are each independently a monovalent aliphatic hydrocarbon group with 1 to ₃ carbons, or a monovalent aliphatic hydrocarbon group with 6 to 10 carbons. valent aromatic hydrocarbon group. Alternatively, from the viewpoint of heat resistance and residual stress, it is preferable that a part of R ₃ and R ₄ in each formula of the present disclosure be a phenyl group.

In a preferred embodiment, the polyvalent compound contains tetracarboxylic dianhydride and diamine. In a preferred embodiment, the polyvalent compound contains tetracarboxylic dianhydride, dicarboxylic acid, and diamine.

<Tetracarboxylic dianhydride>

Tetracarboxylic dianhydride, which is an example of a polyvalent compound contained in a polymerization raw material, is preferably selected from aromatic tetracarboxylic acid having 8 to 36 carbon atoms from the viewpoint of reduction in YI value and total light transmittance. A compound of an acid dianhydride and an alicyclic tetracarboxylic dianhydride having 6 to 36 carbon atoms.

More specifically, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5-(2,5-dioxotetrahydro-3 -furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride (hereafter, also referred to as PMDA), 1,2,3,4-benzenetetracarboxylic dianhydride , 3,3',4,4'-benzophenone tetracarboxylic dianhydride (hereinafter, also referred to as BTDA), 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3 ,3',4,4'-Biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (hereinafter also referred to as DSDA) , 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic anhydride Phthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1, 3-Trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene- 4,4'-diphthalic acid dianhydride, 4,4'-oxodiphthalic acid dianhydride (hereinafter, also referred to as ODPA), thio-4,4'-diphthalic acid di anhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxybenzene oxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl ]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl ]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane Dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (hereinafter also referred to as BPADA), bis(3,4-dicarboxyphenoxy)bis Methylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalene tetra Carboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-Anthracene tetracarboxylic dianhydride, 1,2,7,8-Phenanthrene tetracarboxylic dianhydride, Ethylene tetracarboxylic dianhydride, 1,2,3,4-Butane tetracarboxylic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as CBDA), cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic Carboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter referred to as CHDA), 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, Methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-di Carboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis (Cyclohexane-1,2-dicarboxylic acid) dianhydride, Oxo-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, Thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]octane -7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione -6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- 1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (hereinafter also referred to as TAHQ), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (hereinafter also referred to as BPAF), and the like.

Among them, BTDA and PMDA are preferable from the viewpoint of reduction in CTE, improvement in chemical resistance, improvement in glass transition temperature (Tg), and improvement in mechanical elongation. In addition, 6FDA, ODPA, and BPADA are preferable from the viewpoint of reduction in yellowness index, reduction in birefringence, and improvement in mechanical elongation. In addition, BPDA is preferable from the viewpoint of reduction in residual stress, reduction in yellowness index, reduction in birefringence, improvement in chemical resistance, improvement in Tg, and improvement in mechanical elongation. In addition, CHDA is preferable from the viewpoint of reduction in residual stress and reduction in yellowness index. Among them, from the standpoint of high chemical resistance, reduction in residual stress, reduction in yellowness index, reduction in birefringence, and improvement in total light transmittance, it is preferable to use in combination exhibiting high chemical resistance, high Tg, and low CTE. BPDA of stiff structure and tetracarboxylic dianhydride selected from the group consisting of 6FDA, ODPA and CHDA with low yellowness index and birefringence.

Among them, in addition to the above-mentioned effects, from the viewpoint of high elongation, improvement of chemical resistance, and high Young's modulus, it is preferable that the site derived from BPDA is 20 mol% or more of all sites derived from acid dianhydride, More preferably, it is 50 mol% or more, More preferably, it is 80 mol% or more, It may be 100%.

<Dicarboxylic acid>

In addition, for the resin precursor in this embodiment, in addition to the above-mentioned tetracarboxylic dianhydride, the improvement in mechanical elongation, the improvement in glass transition temperature, and the reduction in yellowness index are adjusted within the range that does not impair performance. For the purpose of copolymerizing dicarboxylic acid and introducing a polyamide component for the purpose of such properties, it is possible to make a heat-cured film into a polyamide-imide. Examples of such dicarboxylic acids include aromatic ring-containing dicarboxylic acids and alicyclic dicarboxylic acids. In particular, from the viewpoint of reduction in YI value and total light transmittance, it is preferable to select dicarboxylic acids having 8 carbon atoms. At least one compound selected from the group consisting of aromatic dicarboxylic acids with ∼36 carbon atoms and alicyclic dicarboxylic acids with 6 to 34 carbon atoms. Specifically, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulfonyl bisbenzoic acid, 3,4 '-Sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxobisbenzoic acid, 3,4'-oxobisbenzoic acid, 3,3'-oxobisbenzoin acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-Dimethyl-4,4'-biphenyl dicarboxylic acid, 2,2'-Dimethyl-3,3'-biphenyl dicarboxylic acid, 9,9-bis(4-(4 -carboxyphenoxy)phenyl)fluorene, 9,9-bis(4-(3-carboxyphenoxy)phenyl)fluorene, 4,4'-bis(4-carboxyphenoxy)biphenyl, 4 ,4'-bis(3-carboxyphenoxy)biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenoxy)biphenyl, 3,3'-bis(4-carboxyphenoxy)biphenyl, 3,3'-bis(3-carboxyphenoxy)biphenyl, 4,4'-bis(4-carboxyphenoxy)-p Terphenyl, 4,4'-bis(4-carboxyphenoxy)-m-terphenyl, 3,4'-bis(4-carboxyphenoxy)-p-terphenyl, 3,3'-bis(4- Carboxyphenoxy)-p-terphenyl, 3,4'-bis(4-carboxyphenoxy)-m-terphenyl, 3,3'-bis(4-carboxyphenoxy)-m-terphenyl, 4, 4'-bis(3-carboxyphenoxy)-p-terphenyl, 4,4'-bis(3-carboxyphenoxy)-m-terphenyl, 3,4'-bis(3-carboxyphenoxy) -P-terphenyl, 3,3'-bis(3-carboxyphenoxy)-p-terphenyl, 3,4'-bis(3-carboxyphenoxy)-m-terphenyl, 3,3'-bis( 3-carboxyphenoxy)-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'- Benzophenone dicarboxylic acid, 1,3-benzenediacetic acid, 1,4-benzenediacetic acid, 5-aminoisophthalic acid derivatives described in International Publication No. 2005/068535 pamphlet, and the like. When these dicarboxylic acids are actually copolymerized in a polymer, they can be used in the form of acid chlorides or active esters derived from thionyl chloride or the like.

Among them, terephthalic acid is particularly preferable from the viewpoint of reduction in YI value and improvement in Tg. When using dicarboxylic acid instead of tetracarboxylic acid, it is preferable that the molar number of dicarboxylic acid is 50 mol% or less with respect to the total sum of dicarboxylic acid and tetracarboxylic acid from a chemical-resistant viewpoint.

<Diamine>

The diamine contained in a polymerization component contains the diamine represented by General formula (1). The diamine represented by general formula (1) can comprise the site originating in the diamine of the unit 1 mentioned later, for example. Among the resin precursors, from the viewpoint of obtaining a suitable yellow index of polyimide film, low birefringence, improvement of total light transmittance, reduction of residual stress with inorganic film, high Tg and high breaking strength The portion derived from the diamine represented by the general formula (1) is preferably 20 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol% or more of all the diamine-derived sites.

In addition, the diamine may contain a divalent silicon group-containing diamine (hereinafter, simply referred to as a silicon-containing diamine) having a silicon number of 2 to 100. As the silicon-containing diamine, for example, diamino (poly)siloxane represented by the following general formula (9) is suitable,

{In the formula, there are a plurality of R ₂ each independently being a divalent aliphatic hydrocarbon with 3 to 20 carbons, or a divalent aromatic group, R ₃ and R ₄ each independently being a monovalent group with 1 to 20 carbons Organic group, l is an integer of 3-50. }. Such a diamine can constitute the unit 2 described later, for example.

Preferable structures of R ₂ in the above general formula (9) include methylene, ethylene, propylene, butylene, and phenylene. In addition, suitable examples of R ₃ and R ₄ in the above general formula (9) include methyl, ethyl, propyl, butyl, and phenyl, and particularly preferably at least a part of them is phenyl.

As the compound represented by the above-mentioned general formula (9), specifically, both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average molecular weight 1300)), two-terminal amino-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-161A (number average molecular weight 1600), X22-161B (number average Average molecular weight 3000), KF8021 (number average molecular weight 4400), Dow Corning Toray Co., Ltd.: BY16-835U (number average molecular weight 900), CHISSO CORPORATION: SilaplaneFM3311 (number average molecular weight 1000)), etc. Among them, from the viewpoint of improvement in chemical resistance and improvement in Tg, methylphenyl silicone oil modified with both terminal amines is particularly preferable.

In addition, the diamine may also contain a group selected from 2,2'-bis(trifluoromethyl)benzidine (hereinafter also referred to as TFMB), 4,4'-(or 3,4'-, 3,3'- , 2,4'-) diaminodiphenyl ether, 4,4'- (or 3,3'-) diaminodiphenyl sulfone, 4,4'- (or 3,3'-) diaminodiphenyl Thioether, 4,4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-bis(4-aminophenoxy)phenyl sulfone, 4,4'-bis (3-aminophenoxy)phenylsulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4 -aminophenoxy)benzene, 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,2'-bis(4-aminophenyl)propane, 2,2',6,6'-tetramethyl-4,4'-diaminobiphenyl, 2,2',6 ,6'-tetrafluoromethyl-4,4'-diaminobiphenyl, bis{(4-aminophenyl)-2-propyl}1,4-benzene, 9,9-bis(4-amino phenyl)fluorene, 9,9-bis(4-aminophenoxyphenyl)fluorene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine and 3,5-bis Aminobenzoic acid, etc., 2,6-diaminopyridine, 2,4-diaminopyridine, bis(4-aminophenyl-2-propyl)-1,4-benzene, 3,3'-bis(trifluoro Methyl)-4,4'-diaminobiphenyl (3,3'-TFDB), 2,2'-bis[3(3-aminophenoxy)phenyl]hexafluoropropane (3-BDAF) , 2,2'-bis[4(4-aminophenoxy)phenyl]hexafluoropropane (4-BDAF), 2,2'-bis(3-aminophenyl)hexafluoropropane (3,3' -6F), and one or more of the group consisting of 2,2'-bis(4-aminophenyl)hexafluoropropane (4,4'-6F). These diamines can constitute the site derived from the diamine of the unit 3 mentioned later. Among them, 1,4-cyclohexanediamine and TFMB are most preferable from the viewpoint of reduction in yellowness index, reduction in CTE, and reduction in YI value.

The resin precursor more preferably contains the following units 1 and 2.

Unit 1 has at least a structure represented by the following general formula (4):

{In the formula, there are a plurality of R ₁ each independently a hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and a plurality of X ₁ that may exist are each independently a carbon number 4 ~32 tetravalent organic groups, and n is an integer of 1-100. };

This unit 2 has the structure represented by the following general formula (5) or the structure represented by the following general formula (6), or has the structure represented by the general formula (5) and the structure represented by the general formula (6) Structure both:

{In the formula, there are a plurality of R ₁ each independently hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and a plurality of R ₂ are each independently a carbon number of 3 to 20 20 divalent aliphatic hydrocarbons or divalent aromatic groups, R ₃ and R ₄ are each independently a monovalent organic group with 1 to 20 carbon atoms, and there may be multiple X ₂ each independently with 4 carbon atoms ~32 tetravalent organic groups, l is an integer of 3-50, and m is an integer of 1-100. },

{In the formula, there are multiple R ₁ each independently hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and multiple R ₃ and R ₄ are each independently carbon A monovalent organic group with a number of 1 to 20, a plurality of R ₈ are each independently a trivalent aliphatic hydrocarbon with a carbon number of 3 to 20, or a trivalent aromatic group, p is an integer of 1 to 100, and q It is an integer of 3 to 50. }.

In general formulas (4) and (6), the diamine-derived site may be derived from a group selected from, for example, 4,4-(diaminodiphenyl)sulfone, 3,4-(diaminodiphenyl)sulfone and One or more diamines from the group consisting of 3,3-(diaminodiphenyl)sulfone. In the general formulas (4) and (5), the parts derived from acid anhydrides are respectively derived from acid dianhydrides having a tetravalent organic group X ₁ (X ₁ is as defined above) and having a tetravalent organic group X ₂ (X ₂ acid dianhydrides as defined above). The diamine-derived site in the structure represented by general formula (5) is derived from diamino (poly)siloxane represented by general formula (9).

From the standpoint of heat resistance, reduction in YI value, and total light transmittance, the unit 1 and the unit 2 are preferably 60 mol% or more based on the total amount of sites derived from the acid dianhydride of the unit 1 and the unit 2. Preferably at least 65 mol %, more preferably at least 70 mol %, contains at least one or more compounds selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA). The site is derived from the group consisting of 4,4'-oxodiphthalic anhydride (ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), cyclohexane -1,2,4,5-tetracarboxylic dianhydride (CHDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis( A site in which at least one or more sites from the group consisting of trimellitic acid monoester anhydride (TAHQ) and 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF) are combined.

In the resin precursor of the present embodiment, the total mass of the unit 1 and the unit 2 is preferably 30% by mass based on the total mass of the resin precursor from the viewpoint of reduction in YI value, reduction in birefringence, and improvement in Tg. As mentioned above, from a viewpoint of the reduction of a birefringence, it is more preferable that it is 70 mass % or more. Most preferably, it is 100% by mass.

In addition, the resin precursor of the present embodiment may further contain a unit 3 having a structure represented by the following general formula (7):

{In the formula, there are a plurality of R ₁ each independently a hydrogen atom, a monovalent aliphatic hydrocarbon with 1 to 20 carbons, or a monovalent aromatic group, and a plurality of X ₃ that may exist are each independently a carbon number 4 ∼32 divalent organic groups, there may be a plurality of X ₄ each independently a tetravalent organic group with 4-32 carbons, and t is an integer of 1-100. }.

The structure of unit 3 is as follows, the diamine-derived part is a diamine other than a compound selected from the group consisting of 4,4-DAS, 3,4-DAS, 3,3-DAS, and silicon-containing diamines parts.

In unit 3, R ₁ is preferably a hydrogen atom. In addition, _X3 is preferably a divalent aromatic group or an alicyclic group from the viewpoint of heat resistance, reduction in YI value, and total light transmittance. In addition, X ₄ is preferably a divalent aromatic group or an alicyclic group from the viewpoint of heat resistance, reduction in YI value, and total light transmittance. Among them, X ₃ is preferably a residue having a structure in which an amino group has been removed from 2,2'-bis(trifluoromethyl)benzidine. The organic groups X ₁ , X ₂ and X ₄ may be the same as or different from each other.

From the viewpoint of reducing the oxygen dependence of the YI value and the total light transmittance, the mass ratio of the unit 3 in the resin precursor of the present embodiment is 80% by mass or less, preferably 70% by mass or less in the entire resin structure.

Regarding the resin precursor of this embodiment, the resin obtained by heating and curing the resin precursor at 300 to 500° C. in an inert atmosphere (for example, nitrogen or argon atmosphere), or the resin precursor in The resin obtained by heating and curing at 350°C in an inert atmosphere preferably has at least one glass transition temperature in the range of -150°C to 0°C and at least one glass transition temperature in the range of 150°C to 380°C, and has a glass transition temperature greater than The range of 0°C and less than 150°C does not have a glass transition temperature. From the viewpoint of achieving a good balance between residual stress and total light transmittance, it is preferable that the glass transition temperature exists in the range of -150°C to 0°C and in the range of 150°C to 380°C. From the viewpoint of heat resistance, the glass transition temperature in the range of 150°C to 380°C is more preferably in the range of 200 to 380°C, still more preferably in the range of 250 to 380°C. Having the block 1 and block 2 described later in the resin precursor is advantageous for the formation of such a resin precursor.

From the viewpoint of improving heat resistance, the resin precursor of the present embodiment is preferably composed of block 1 mainly composed of unit 1 and block 2 mainly composed of unit 2 . In addition, the resin precursor may include the aforementioned unit 3 in the block 1 . These blocks may be bonded alternately or sequentially in the polymer chain.

The above-mentioned block 1 contributes to the development of Tg in the range of 150 to 380° C. for the polyimide obtained by heating and curing the resin precursor of the present embodiment. Therefore, the block 1 is preferably a block formed only by repeating the above-mentioned unit 1, but it does not exclude the case where the unit 3 other than the unit 1 is contained within the range where the target Tg can be expressed.

Similarly, the above-mentioned block 2 contributes to expressing Tg in the range of -150-0 degreeC with respect to the polyimide obtained by heat-hardening the resin precursor of this embodiment. Therefore, the block 2 is preferably a block formed only by repeating the above-mentioned unit 2, but it does not exclude the case where units other than the unit 2 are included within the range in which the target Tg can be expressed.

In the resin precursor having block 1 and block 2, the sum of the repeating numbers of unit 1 and unit 3 in block 1 is preferably 2 to 500 on average, more preferably 5 to 300, most preferably 10 ~200. In addition, the number of repetitions of the unit 2 in the block 2 is preferably 1.1 to 300, more preferably 1.1 to 200, and most preferably 1.2 to 100 on average per molecule. When the sum of the repeating numbers of the unit 1 and the unit 3 in the block 1 is 500 or less, and the repeating number of the unit 2 in the block 2 is 300 or less, the solubility of the resin precursor to the solvent becomes good, which is preferable.

The ratio defined by the sum of the repeating numbers of unit 1 and unit 3 in block 1 divided by the repeating number of unit 2 in block 2 (hereinafter also referred to as unit ratio) may vary depending on the type of raw material used, Although the molecular weight varies depending on the molecular weight, it is preferably 0.5-100, and more preferably 10-50. As mentioned above, the polyimide which is a cured product of the resin precursor having block 1 and block 2 can have the advantage that A has a glass transition derived from block 1 in the range of 150°C to 380°C Temperature, the range B from -150°C to 0°C has a glass transition temperature derived from block 2, and the range C between this range A and this range B has no glass transition temperature. When the value of the said unit ratio is 0.5 or more, the heat resistance of the polyimide resin after hardening is sufficient, and it is preferable. Moreover, when it is 100 or less, residual stress can be reduced, and it is preferable.

On the other hand, when a high-molecular-weight organosilicon compound (specifically, an organosilicon compound with an average molecular weight of 3,000 or more) is used as the silicon-group-containing compound in the polymerization component, even if such a block copolymer as described above is not formed, the obtained The polyimide also maintains a high glass transition temperature and exhibits low residual stress with inorganic films. It is considered that if a high-molecular-weight organosilicon compound is used, the organosilicon unit itself is a long-chain siloxane structure, which can play the same role as the above-mentioned block structure. Here, when the organosilicon compound has a high molecular weight, the concentration of functional groups decreases, so that the above-mentioned high glass transition temperature and low residual stress can be exhibited even if the number of moles charged is small.

For example, when the high-molecular-weight organosilicon compound is a diamine, the resin precursor generates a unit 1 of the general formula (4) derived from (diaminodiphenyl)sulfone and a general formula (4) derived from the organosilicon diamine. 5) In addition to the copolymer of unit 2, there is also such a polyimide precursor mixture, that is, a blend, in which the polyimide precursor of unit 1 exists alone (that is, the unit 2 is not copolymerized).

Therefore, the present disclosure also includes a precursor mixture including the above-mentioned resin precursor of the present embodiment and an additional resin precursor (for example, the polyimide precursor of the above-mentioned unit 1 alone). Here, as a specific example of the independent polyimide precursor of the unit 1, a resin precursor having a structure represented by the following general formula (8):

{In the formula, there may be a plurality of X ₃ each independently being a tetravalent organic group with 4 to 32 carbons, and a plurality of R ₁ each independently being a hydrogen atom, a monovalent aliphatic group with 1 to 20 carbons a hydrocarbon group or a monovalent aromatic group, and r is an integer of 1-100. }.

On the other hand, when the high-molecular-weight organosilicon compound is an example other than diamine, for example, L ₁ , L ₂ and L ₃ in the general formula (3) are each independently an acid anhydride group, a carboxyl group, an acid ester group, organosilicon compounds such as acyl halide, hydroxyl, epoxy, or mercapto.

When the polymerization component in the resin precursor of this embodiment contains a high-molecular-weight organosilicon compound, the polyimide that is the cured product of the resin precursor still maintains a relatively high glass transition temperature in the range of 150°C to 380°C. , and can achieve the special characteristics of significantly reducing the residual stress between the inorganic film.

The number average molecular weight of the resin precursor of the present embodiment is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 7,000 to 300,000, particularly preferably 10,000 to 250,000. From the viewpoint of obtaining good heat resistance and strength (such as strong elongation), the molecular weight is preferably 3000 or more, and from the viewpoint of obtaining good solubility in solvents, it can be processed according to the desired film when coating or the like. From the viewpoint of thick coating without leakage, it is preferably 1,000,000 or less. From the viewpoint of obtaining high mechanical elongation, the molecular weight is preferably 50,000 or more. In the present disclosure, the number average molecular weight is a value obtained by converting to standard polystyrene using gel permeation chromatography.

In a preferred embodiment, a part of the resin precursor may also be imidized.

The resin precursor of this embodiment can be formed into a polyimide resin as follows: as a glass on the high temperature side, it can withstand heat resistance in the manufacturing process of a display equipped with a TFT element device on a colorless and transparent polyimide substrate. The transition temperature ranges from 150°C to 380°C, and the residual stress with the inorganic film is 25 MPa or less at a film thickness of 10 μm. In a more preferable embodiment, the resin precursor can be a polyimide resin having a glass transition temperature of 240° C. to 380° C. and a residual stress with the inorganic film of 20 MPa or less at a film thickness of 10 μm. When a polyimide resin has a glass transition temperature of -150-0 degreeC, since this temperature is below room temperature, it does not affect the heat resistance required in the actual display manufacturing process.

Moreover, in a preferable aspect, a resin precursor has the following characteristics.

A resin obtained by dissolving a solution obtained by dissolving a resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) on the surface of the support has a yellowness index of 7 or less at a film thickness of 20 μm After development, the solution is heated (eg, 1 hour) at 300-500° C. (eg, 350° C.) under a nitrogen atmosphere to imidize the resin precursor.

A residual stress of 25 MPa or less at a film thickness of 10 μm of a resin obtained by dissolving a resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) on the surface of the support After development, the solution is heated (eg, 1 hour) at 300-500° C. (eg, 350° C.) under a nitrogen atmosphere to imidize the resin precursor.

<Manufacture of resin precursor>

Next, the synthesis method of the resin precursor of this embodiment is demonstrated. For example, in the case where the resin precursor of the present embodiment is composed of the aforementioned block 1 and block 2, the polyimide precursor corresponding to each block is prepared separately, and then the two are mixed, The resin precursor of this embodiment can be obtained by carrying out condensation reaction. Here, the molar ratio of each raw material, such as the molar ratio of tetracarboxylic dianhydride and diamine, is adjusted so that the condensation reaction of the two blocks can be carried out, and the terminal group of the polyimide precursor of one block is In the case of a carboxylic acid, the terminal group of the polyimide precursor of the other block is an amino group or the like. This method can synthesize|combine the polyimide precursor which has a more preferable complete block property.

On the other hand, tetracarboxylic dianhydride, which is the raw material for polymerization, is common between block 1 and block 2, and aromatic diamine is used as the raw material of block 1, and highly reactive diamine is used as the raw material of block 2. In the case of a silicon-containing diamine, there may be a possibility of a synthetic method utilizing poor reactivity of two kinds of diamines. For example, a polyimide precursor having some block properties can be produced by simultaneously adding an aromatic diamine and a silicon-containing diamine to tetracarboxylic dianhydride prepared in advance, and performing a condensation reaction. Although this method cannot synthesize|combine the block polyimide precursor which has complete block property, it can synthesize|combine the polyimide precursor which has block property. The blockiness here means that the glass transition temperature corresponding to each block is observed for the heat-cured polyimide resin, for example, the polyimide resin shows in the aforementioned range A and range B One selected from the group consisting of 4,4-(diaminodiphenyl)sulfone, 3,4-(diaminodiphenyl)sulfone and 3,3-(diaminodiphenyl)sulfone The glass transition temperature of block 1 derived from the polycondensate of tetracarboxylic anhydride and the glass transition temperature of block 2 derived from the polycondensate of silicon-containing diamine and tetracarboxylic anhydride.

As described above, in the resin precursor of the present embodiment, the polyimide resin obtained by heating and curing the resin precursor has vitrification recognizable in the range A on the high temperature side and the range B on the low temperature side, respectively. Blockiness at the transition temperature level is advantageous, and this advantage can be obtained even if the polyimide resin does not have complete blockiness. In addition, for the aforementioned advantages of the resin precursor having blocks 1 and 2, if no glass transition temperature is recognized in the range C between the range A and the range B, it is also possible to contain Units other than segment 2.

In addition, adding N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal to the above polyamic acid and heating, by partially or completely Esterification of the carboxylic acid can improve the viscosity stability of the solution containing the resin precursor and the solvent when stored at room temperature. These ester-modified polyamic acids can also be obtained as follows. First, the above-mentioned tetracarboxylic anhydride is reacted with a monohydric alcohol of 1 equivalent to the acid anhydride group, and then reacted with a dehydration condensation agent such as thionyl chloride or biscyclohexylcarbodiimide. , followed by a condensation reaction with a diamine.

<Resin composition>

Another aspect of this invention provides the resin composition containing the said resin precursor or precursor mixture, and a solvent. The resin composition is typically a varnish.

As a more preferable aspect, the resin composition can dissolve the carboxylic acid component and the diamine component in a solvent such as an organic solvent and react them to form a polyamic acid solution containing a polyamic acid and a solvent, which is one form of a resin precursor. form for manufacture. Here, the conditions during the reaction are not particularly limited, for example, the reaction temperature is -20 to 150°C, and the reaction time is 2 to 48 hours. In order to sufficiently advance the reaction of the silicon group-containing compound, it is preferable to heat at 120° C. for about 30 minutes. In addition, it is preferable to use an inert atmosphere such as argon gas or nitrogen gas during the reaction.

In addition, the solvent will not be particularly limited as long as it dissolves the polyamic acid. Known reaction solvents are selected from dimethylene glycol dimethyl ether (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl Acetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate, Equamide M100 (trade name: manufactured by Idemitsu Retail Marketing Co. Ltd.), and Equamide B100 (trade name: Idemitsu Retail Marketing Co. Ltd. . System) in more than one polar solvent is useful. Among them, NMP, DMAc, Equamide M100, and Equamide B100 are preferred. In addition, a low boiling point solution such as tetrahydrofuran (THF) or chloroform, or a low absorption solvent such as γ-butyrolactone can also be used.

In addition, in the resin composition of the present invention, when the obtained polyimide is formed into an element such as a TFT, in order to impart sufficient adhesion to the support, it is preferable to contain 0.01 to 2% by mass of % of alkoxysilane compounds such a composition.

With respect to 100 mass % of the resin precursor, by making the content of the alkoxysilane compound 0.01 mass % or more, good adhesion with the support can be obtained, and from the viewpoint of the storage stability of the resin composition, the alkoxysilane The content of the oxysilane compound is preferably 2% by mass or less. The content of the alkoxysilane compound is more preferably 0.02 to 2% by mass, still more preferably 0.05 to 1% by mass, still more preferably 0.05 to 0.5% by mass, particularly preferably 0.1 to 0.5% by mass based on the resin precursor.

Examples of alkoxysilane compounds include 3-ureidepropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, phenyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyl Tributoxysilane, γ-Aminoethyltriethoxysilane, γ-Aminoethyltrimethoxysilane, γ-Aminoethyltripropoxysilane, γ-Aminoethyltributoxysilane, γ -Aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, etc. In addition, they can also be used in combination more than one species.

After producing the above-mentioned varnish, a part of the polymer may be dehydrated imidized without causing polymer precipitation by heating the solution at 130 to 200° C. for 5 minutes to 2 hours. The imidation rate can be controlled by controlling temperature and time. Viscosity stability at room temperature storage of the resin precursor solution can be improved by partial imidization. The range of the imidation rate is preferably 5% to 70% from the viewpoint of the solubility of the resin precursor in the solution and the storage stability of the solution.

Moreover, in a preferable aspect, a resin composition has the following characteristics.

The yellowness index at 20 μm film thickness of the resin obtained by developing the resin composition on the surface of the support body by developing the resin composition at 300° C. to 500° C. under a nitrogen atmosphere shows a yellowness index of 7 or less. It is obtained by imidizing the resin precursor contained in a resin composition by heating (or by heating at 350 degreeC in nitrogen atmosphere).

The residual stress at 10 μm film thickness of the resin obtained by developing the resin composition on the surface of the support by developing the resin composition at 300° C. to 500° C. under a nitrogen atmosphere shows a residual stress of 25 MPa or less. It is obtained by imidizing the resin precursor contained in a resin composition by heating (or by heating at 350 degreeC in nitrogen atmosphere).

<Resin film>

Another aspect of the present invention provides a resin film that is a cured product of the aforementioned resin precursor, or a cured product of the aforementioned precursor mixture, or a cured product of the aforementioned resin composition.

In addition, another aspect of the present invention provides a method for producing a resin film including:

The step of developing the aforementioned resin composition on the surface of the support;

A step of heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film; and

A step of peeling the resin film from the support.

In a preferable aspect of the manufacturing method of a resin film, the polyamic-acid solution obtained by dissolving an acid dianhydride component and a diamine component in an organic solvent and making them react can be used as a resin composition.

Here, the support is, for example, an inorganic substrate such as a glass substrate such as an alkali-free glass substrate, and is not particularly limited.

More specifically, the above-mentioned resin composition is developed on the adhesive layer formed on the main surface of the inorganic substrate, dried, and cured at a temperature of 300 to 500° C. in an inert atmosphere to form a resin film. Finally, the resin film is peeled off from the support.

Here, examples of the spreading method include known coating methods such as spin coating, slit coating, and blade coating. In addition, the heat treatment is as follows. After the polyamic acid solution is developed on the adhesive layer, heat treatment is performed at a temperature of 300° C. or less for 1 minute to 300 minutes mainly for the purpose of desolventization, and further at 300° C. to 550° C. under an inert atmosphere such as nitrogen. The temperature of °C is heat-treated for 1 minute to 300 minutes to polyimide the resin precursor. In the case of producing a conventional colorless and transparent polyimide film, it is necessary to control the oxygen concentration in the oven to 100 ppm or less from the viewpoint of the reduction of the YI value and the total light transmittance. For the precursor, it is sufficient to control it below 500ppm. From the standpoint of reducing the YI value and improving the total light transmittance, the oxygen concentration is preferably 1000 ppm or less.

Moreover, the thickness of the resin film of this embodiment is not specifically limited, It is preferable that it is the range of 10-200 micrometers, and it is more preferable that it is 10-50 micrometers.

The resin film of the present embodiment preferably has a yellowness index of 7 or less in a film thickness of 20 μm. In addition, the residual stress is preferably 25 MPa or less at a film thickness of 10 μm. In particular, it is further preferable that the yellowness index at a film thickness of 20 μm is 7 or less, and the residual stress at a film thickness of 10 μm is 25 MPa or less. Such characteristics are favorably realized by, for example, imidizing the resin precursor of the present disclosure at 300° C. to 500° C., more particularly at 350° C., under a nitrogen atmosphere.

<laminate>

Another aspect of the present invention provides a laminate including a support and a resin film formed on the surface of the support that is a cured product of the aforementioned resin composition.

In addition, another aspect of the present invention provides a method for producing a laminate including:

A step of spreading the aforementioned resin composition on the surface of the support; and

A step of heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film, thereby obtaining a laminate including the support and the resin film.

Such a laminate can be produced, for example, by not peeling the resin film formed in the same manner as in the aforementioned method of producing the resin film from the support.

This laminate is used, for example, in the manufacture of flexible devices. More specifically, a semiconductor device is formed on a polyimide film, and then the support is peeled off to obtain a flexible device including a flexible transparent substrate formed of a polyimide film.

Therefore, another aspect of the present invention provides a flexible device material comprising the aforementioned resin precursor or the aforementioned precursor mixture.

As described above, since the resin precursor of the present embodiment has a specific structure, it is possible to form a resin film that does not become cloudy without a combination of special solvents. In addition, the yellowness index (YI value) and the total light transmittance of the obtained resin film are less dependent on the oxygen concentration during curing. In addition, the residual stress generated between the resin thin film and the inorganic film is low, has a practical glass transition temperature that can withstand the TFT manufacturing process, has excellent mechanical properties, and has chemical resistance that can withstand the photolithography process. Therefore, the resin precursor is suitable for a transparent substrate of a flexible display.

When it demonstrates in more detail, when forming a flexible display, a glass substrate is used as a support body, a flexible substrate is formed thereon, and TFT etc. are formed on it. The process of forming a TFT on a substrate is typically carried out at a wide range of temperatures from 150 to 650°C, but in order to achieve the desired performance, TFT-IGZO ( InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si-TFT).

At this time, if the residual stress generated between the flexible substrate and the polyimide film is high, it will expand during the high-temperature TFT process and then shrink when cooled at room temperature. During this process, warping and damage of the glass substrate will occur, and the flexible substrate will break from the glass. Problems such as substrate peeling. In general, glass substrates have a smaller coefficient of thermal expansion than resins, so residual stress is generated between them and flexible substrates. In the resin film of the present embodiment, considering this point, the residual stress generated between the resin film and the glass is preferably 25 MPa or less based on a film thickness of 10 μm.

In addition, for the resin film of the present embodiment, it is preferable that the yellowness index is 7 or less based on the thickness of the film of 20 μm, and when the transmittance is measured with an ultraviolet spectrophotometer, the yellowness index is 7 or less when the thickness of the film is 20 μm. The transmittance is above 85%. In addition, it is advantageous to stably obtain a resin film with a low YI value if the oxygen concentration dependence in the oven used for making the thermosetting film is small, and the YI value of the thermosetting film is stable at an oxygen concentration of 500 ppm or less, and it is preferable .

In addition, the resin film of the present embodiment preferably has a mechanical elongation of 30% or more based on a film thickness of 20 μm from the standpoint of excellent breaking strength during handling of flexible substrates, thereby improving yield.

In addition, the resin thin film of the present embodiment preferably has a glass transition temperature of 250° C. or higher in order not to cause softening of the resin substrate at a temperature at which a TFT element is produced.

Moreover, it is preferable that the resin film of this embodiment has the chemical resistance which can withstand the photoresist stripping liquid in the photolithography process used when manufacturing a TFT element.

In addition, there are two types of light extraction methods for flexible displays: a top-emission method that extracts light from the front side of a TFT element, and a bottom-emission method that extracts light from the back side. The top-emission method is easy to increase the aperture ratio because the TFT element is not in the way; the bottom-emission method is easy to manufacture because the position alignment is easy. If the TFT element is transparent, the aperture ratio can be increased also in the bottom emission method, so the adoption of the bottom emission method, which is easy to manufacture large-scale organic EL flexible displays, is expected. When using a colorless transparent resin substrate for a bottom-emission method, since the resin substrate appears on the viewing side, from the viewpoint of improving image quality, optical isotropy, that is, the property derived from birefringence is required. The optical path difference (Rth) in the thickness direction is low. In addition, when the top-emission method is used, low Rth is not required, but a material with low Rth is preferable from the viewpoint that both methods can be commonly used. Specifically, based on a film thickness of 20 μm, it is preferably 200 nm or less, more preferably 90 nm or less, further preferably 80 nm or less, particularly preferably 50 nm or less. If Rth is 100nm or less, and further 90nm or less, it will not only satisfy the performance required for application to transparent substrates for top-emission flexible displays, but also satisfy the requirements for transparent substrates for bottom-emission flexible displays and electrodes for touch panels. properties required for the application in the substrate.

Another aspect of this invention provides the polyimide resin film used for manufacture of a display board|substrate, and Rth at the time of thickness 20 micrometers is 20-90 nm.

In addition, another aspect of the present invention provides a method for manufacturing a display substrate, which includes:

A step of spreading a resin composition comprising a polyimide precursor on the surface of the support;

A step of heating the support and the resin composition to imidize the polyimide precursor to form the aforementioned polyimide resin film;

A process of forming an element on the polyimide resin film; and

A step of peeling the polyimide resin film forming the element from the support.

The resin film of the present embodiment that satisfies the above physical properties can be used in applications where use is limited due to the yellow color of conventional polyimide films, and is particularly suitable for use as a colorless and transparent substrate for flexible displays. Furthermore, even in light-diffusing sheets and coating films such as protective films or TFT-LCDs (for example, intermediate layers of TFT-LCDs, gate insulating films, and liquid crystal alignment films), ITO substrates for touch panels, and replacements for smartphones It can also be used in fields requiring colorless transparency and low birefringence, such as resin substrates for cover glasses. When the polyimide of this embodiment is used as a liquid crystal aligning film, it contributes to the increase of an aperture ratio, and can manufacture TFT-LCD of a high contrast ratio.

Resin films and laminates produced using the resin precursors of this embodiment can be used, for example, in the manufacture of semiconductor insulating films, TFT-LCD insulating films, electrode protective films, and flexible devices, and are particularly suitable as substrates. Here, examples of flexible devices include flexible displays, flexible solar cells, flexible touch panel electrode substrates, flexible lighting, and flexible batteries.

Example

Hereinafter, the present invention will be described in more detail based on examples, but these are described for explanation, and the scope of the present invention is not limited to the following examples.

Various evaluations in Examples and Comparative Examples were performed as follows.

(Determination of weight average molecular weight)

The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC) under the following conditions. As a solvent, N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatography) was used, and lithium bromide monohydrate (Wako Pure Chemical Industries, Ltd.) added 24.8 mmol/L before measurement was used. , Ltd., purity 99.5%) and N,N-dimethylformamide of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatography) at 63.2 mmol/L. In addition, a calibration curve for calculating the weight average molecular weight was created using standard polystyrene (manufactured by TOSOH CORPORATION).

Column: Shodex KD-806M (manufactured by SHOWA DENKO K.K.)

Flow rate: 1.0mL/min

Column temperature: 40°C

Pump: PU-2080Plus (manufactured by JASCO CORPORATION)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO CORPORATION) UV-2075Plus (UV-VIS: ultraviolet-visible spectrophotometer, manufactured by JASCO CORPORATION).

(Silicone-containing monomer concentration)

The concentration of the silicon group-containing monomer is calculated from the following formula using the mass of each of the silicon group-containing monomer, polycarboxylic acid or its derivative, and diamine compound used when synthesizing the resin precursor.

Silicon-containing monomer concentration (%)=silicon-containing monomer mass/(silicon-containing monomer mass+polycarboxylic acid or its derivatives mass+diamine compound mass)×100

(Manufacture of laminates and separation films)

The resin composition is coated on the non-alkali glass substrate (thickness 0.7mm) with bar coater, carry out 5 minutes～10 minutes leveling at room temperature, in vertical curing oven (Koyo Lindberg Ltd. manufacture, model VF-2000B ) at 140° C. for 60 minutes, and further heated at 350° C. for 60 minutes under a nitrogen atmosphere to produce a laminate. At this time, the oxygen concentration in the hot air oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and the oxygen concentration dependence of the YI value and the total light transmittance was investigated. The film thickness of the resin composition of the laminate was 20 μm. After curing at 350° C. (curing treatment), the laminate was left to stand at room temperature for 24 hours, and the resin film was peeled from the glass to separate the film. The following evaluations other than the yellowness index and the total light transmittance used a resin film that adjusted the oxygen concentration in a hot air oven to 100 ppm and cured at 350° C. for 60 minutes as a sample.

(Evaluation of Tensile Elongation)

A resin film with a length of 5 x 50 mm and a thickness of 20 μm that was cured at 350°C was stretched at a speed of 100 mm/min using a tensile tester (manufactured by A&D Company, Limited: RTG-1210) to measure the tensile elongation .

(Yellow index, total light transmittance and its dependence on oxygen concentration during curing)

For a resin film with a thickness of 20 μm that was cured at 350°C with the oxygen concentration adjusted to 50ppm, 100ppm, and 500ppm in the oven, yellowness was measured using a D65 light source (Spectrophotometer: SE600) manufactured by NIPPON DENSHOUKUINDUSTRIES Co., Ltd. Index (YI value) and total light transmittance.

(Evaluation of optical path difference (Rth) in the thickness direction)

A resin film with a thickness of 20 μm cured at 350° C. was measured using a retardation birefringence measuring device (manufactured by Oji Scientific Instruments, KOBRA-WR). The wavelength of the measurement light was set to 589 nm.

(Evaluation of glass transition temperature and linear expansion coefficient)

Regarding the measurement of the glass transition temperature (called Tg(1)) and the coefficient of linear expansion (CTE) above the room temperature range, a resin film with a length of 5 × 50 mm and a thickness of 20 μm, which was cured at 350 ° C, was used by Shimadzu Corporation. The thermomechanical analysis device (TMA-50) uses thermomechanical analysis to measure the elongation of the test piece under a load of 5g, a heating rate of 10°C/min, a nitrogen atmosphere (flow rate of 20ml/min), and a temperature range of 50 to 450°C The measurement of the inflection point was obtained as the glass transition temperature, and the CTE of the heat-resistant resin film at 100 to 250° C. was obtained.

It is impossible to measure the glass transition temperature (referred to as Tg(2)) below the room temperature range by the above-mentioned method, so the above-mentioned resin film is used for dynamic viscosity measurement equipment (ORIENTEC Co., LTD., RHEOVIBRONMODELRHEO -1021) Measure the inflection point in the temperature range below the room temperature of the E program (E prime) in the range of -150°C to 400°C, and obtain the inflection point as the glass transition temperature at low temperature.

(Evaluation of residual stress)

Using a residual stress measuring device (manufactured by KLA-Tencor Corporation, model FLX-2320), the resin composition was coated with a bar coater on a 6-inch silicon wafer with a thickness of 625 μm ± 25 μm and the “warpage amount” was measured in advance. After pre-baking at 140°C for 60 minutes, use a vertical curing furnace (manufactured by KoyoLindberg Ltd., model VF-2000B) to perform heat curing treatment at 350°C for 1 hour in a nitrogen atmosphere to produce cured A silicon wafer made of a resin film with a film thickness of 10 μm. The amount of warpage of the wafer was measured using the aforementioned residual stress measuring device, and the residual stress generated between the silicon wafer and the resin film was evaluated.

(Evaluation of chemical resistance test)

Soak a resin film with a thickness of 20 μm cured at 350°C in the NMP layer at room temperature, lift it up every 10 minutes, wash it with ion-exchanged water, observe the surface of the film with a microscope, and check the appearance of the surface of the thermally cured film every 10 minutes. The evaluation of the cracking time was performed up to 300 minutes.

[Example 1]

In a 3L detachable flask equipped with a stirring bar equipped with an oil bath, introduce nitrogen gas, add 1000g of NMP, and add 232.4g of 3,3-(diaminodiphenyl)sulfone (defined as diaminodiphenyl)sulfone while stirring. Amine 1), followed by adding 218.12 g of pyromellitic dianhydride (specified as tetracarboxylic anhydride 1), and stirring at room temperature for 30 minutes. It was heated up to 50° C., and after stirring for 12 hours, 105.6 g of both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400)) ( It is defined as a silicon group-containing diamine) was dissolved in 298 g of NMP, and was added dropwise using a dropping funnel. After heating up to 80 degreeC and stirring for 1 hour, the oil bath was removed, it returned to room temperature, and the NMP solution (henceforth, also referred to as a varnish) of a transparent polyamic acid was obtained. Table 1 shows the composition and the weight average molecular weight (Mw) of the polyamic acid obtained therein. In addition, Table 4 shows the test results of the film cured at 350°C.

[Examples 2-33, 49-58]

In the same manner as in Example 1, the types of diamine 1, tetracarboxylic anhydride 1, and silicon group-containing diamine, and their added masses were changed to those described in Table 1, respectively, and the same operation as in Example 1 was performed to obtain a varnish. In addition, the addition amount of NMP shown in Table 1 and Table 2 represents the total amount of NMP contained in the final varnish, and is the mass containing 298 g of NMP for diluting the silicon group containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1, Table 2, and Table 7, respectively. In addition, the test results of the films cured at 350°C are shown in Table 4, Table 5, and Table 8, respectively. The official compound names of the abbreviated compound names described in Tables 1 to 6 are described below.

3,3-DAS: 3,3-(Diaminodiphenyl)sulfone

4,4-DAS: 4,4-(Diaminodiphenyl)sulfone

3,4-DAS: 3,4-(Diaminodiphenyl)sulfone

PMDA: pyromellitic dianhydride

ODPA: 4,4'-Oxodiphthalic dianhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

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

CHDA: cyclohexane-1,2,4,5-tetracarboxylic dianhydride

DSDA: 3,3’,4,4’-Diphenylsulfonetetracarboxylic dianhydride

BPADA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride

BPAF: 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride

TAHQ: 4,4'-biphenylbis(trimellitic acid monoester anhydride)

BTDA: 3,3’,4,4’-Benzophenone tetracarboxylic dianhydride

TPE-R: 1,3-bis(4-aminophenoxy)benzene

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

FM3311: Both ends amine-modified simethicone (Silaplane FM3311 (number average molecular weight: 1000) manufactured by CHISSO CORPORATION)

TFMB: 2,2’-bis(trifluoromethyl)benzidine

TACl: Trimellitic anhydride chloride

[Example 34]

Into a 3L detachable flask equipped with a stirring bar equipped with an oil bath, introduce nitrogen gas, add 1274g of NMP, and add 4,4'-oxodiphthalic dianhydride (hereinafter referred to as ODPA) (regulated as Tetracarboxylic anhydride 1), while stirring, 105.6 g of both-terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400)) (specified as containing The solution obtained by dissolving silicon-based diamine) in 298g NMP was added dropwise using a dropping funnel. After stirring at room temperature for 1 hour, 149.9 g of 2,2'-bis(trifluoromethyl)benzidine (hereinafter referred to as TFMB) (defined as diamine 2) was added while stirring, and then 116.2 g of g of 3,3-DAS and stirred at room temperature for 1 hr. Next, it heated up at 50 degreeC, added 147.1g of BPDA (prescribed as tetracarboxylic anhydride 2), and stirred for 12 hours. After heating up this to 80 degreeC and stirring for 4 hours, the oil bath was removed, it returned to room temperature, and the NMP solution (henceforth, also referred to as a varnish) of a transparent polyamic acid was obtained. Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid among them. In addition, Table 5 shows the test results of the film cured at 350°C.

[Example 35, 39, 40, 44, 45]

In the same manner as in Example 34, the types of diamine 1, diamine 2, tetracarboxylic anhydride 1, and tetracarboxylic anhydride 2 and their added masses were changed to those described in Table 2, and the same operations as in Example 34 were performed. And get varnish. In addition, the addition amount of NMP shown in Table 2 represents the total amount of NMP contained in the final varnish, and is the mass containing 298 g of NMP for diluting silicon group containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. In addition, the test results of the films cured at 350° C. are shown in Table 5, respectively.

[Example 36]

Into a 3L detachable flask equipped with a stirring bar equipped with an oil bath, introduce nitrogen gas, add 1196g of N-methylpyrrolidone (hereinafter referred to as NMP), and add 232.4g of 3,3-(diaminodi Phenyl)sulfone (specified as diamine 1), after heating to 50°C, added 147.1g of BPDA (specified as tetracarboxylic anhydride 1), and stirred for 30 minutes. Next, 155.1 g of ODPA (specified as tetracarboxylic anhydride 2) was added, and after stirring for 8 hours, 105.6 g of both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (Number average molecular weight 4400)) (regulated as the diamine containing silicon group) was dissolved in 298g NMP, and was added dropwise using a dropping funnel. After heating up to 80 degreeC and stirring for 1 hour, the oil bath was removed, it returned to room temperature, and the NMP solution (henceforth, also referred to as a varnish) of a transparent polyamic acid was obtained. Table 2 shows the composition and the weight average molecular weight (Mw) of the polyamic acid obtained therein. In addition, Table 5 shows the test results of the film cured at 350°C.

[Example 37, 42, 43, 46, 47]

In the same manner as in Example 36, the types of diamine 1, tetracarboxylic anhydride 1, and tetracarboxylic anhydride 2, and their added masses were changed to those described in Table 2, respectively, and the same operation as in Example 36 was performed to obtain a varnish. In addition, the addition amount of NMP shown in Table 2 represents the total amount of NMP contained in the final varnish, and is the mass containing 298 g of NMP for diluting silicon group containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. In addition, the test results of the films cured at 350° C. are shown in Table 5, respectively.

[Example 38]

Into a 3L detachable flask equipped with a stirring bar equipped with an oil bath, nitrogen gas was introduced, 1200g of NMP was added, and 232.4g of 3,3-(diaminodiphenyl)sulfone (specified as diamine 1) was added while stirring. , after heating to 50° C., 40.6 g of terephthaloyl chloride (specified as another monomer component) was dissolved in 200 g of γ-butyrolactone, and then added dropwise and stirred for 30 minutes. Next, 235.4 g of BPDA (specified as tetracarboxylic anhydride 1) was added, and after stirring for 8 hours, 105.6 g of both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 ( Number-average molecular weight 4400)) (specified as diamine containing silicon group) was dissolved in 298g NMP, and was added dropwise using a dropping funnel. After raising the temperature to 80° C. and stirring for 1 hour, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent polyamic acid solution. After adding 1000g of NMP to it for dilution, it was added dropwise to 10L of ion-exchanged water while feeding. After the powder of the polyamide-imide precursor was precipitated, the powder was filtered with a Buchner funnel. The powder was dried under vacuum at 40°C for 48 hours. To the powder thus obtained, 1403 g of NMP was added to obtain an NMP solution of a polyamide-imide precursor. Table 2 shows the composition and the weight average molecular weight (Mw) of the polyamide-imide precursor obtained therein. In addition, Table 5 shows the test results of the film cured at 350°C.

[Example 43, 48]

In the same manner as in Example 38, the types of diamine 1, tetracarboxylic anhydride 1, and other monomer components, and their added masses were changed to those described in Table 2, respectively, and the same operation as in Example 38 was performed to obtain a varnish. In addition, the added amount of NMP shown in Table 2 represents the total amount of NMP contained in the final varnish. The composition and the weight average molecular weight (Mw) of the obtained polyamide-imide precursor are shown in Table 2, respectively. In addition, the test results of the films cured at 350°C are shown in Table 5, respectively.

[Example 59]

Into a 3L detachable flask with a stirring bar equipped with an oil bath, introduce nitrogen gas, add 1000g of NMP, and add 248.30g of 3,3-(diaminodiphenyl)sulfone (defined as diamine 1), then add 275.13g BPDA (specified as tetracarboxylic anhydride 1), stirred at room temperature for 30 minutes. It was heated up to 50° C., and after stirring for 12 hours, 104.58 g of anhydride-modified methylphenyl silicone oil at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-168-P5-B (number average molecular weight 4200)) Dissolve in 298g NMP and add dropwise using a dropping funnel. After heating up to 80 degreeC and stirring for 1 hour, the oil bath was removed, it returned to room temperature, and the NMP solution (henceforth, also referred to as a varnish) of a transparent polyamic acid was obtained. Table 7 shows the composition and the weight average molecular weight (Mw) of the polyamic acid obtained therein. In addition, Table 8 shows the test results of the film cured at 350°C.

[Examples 60-66]

In the same manner as in Example 59, the types of diamine 1, tetracarboxylic anhydride 1, and silicon group-containing diamine and their added masses were changed to those described in Table 1, respectively, and the same operation as in Example 1 was performed to obtain a varnish. . In addition, the addition amount of NMP shown in Table 1 and Table 2 represents the total amount of NMP contained in the final varnish, and is the mass containing 298 g of NMP for diluting the silicon group containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 7, respectively. In addition, the test results of the films cured at 350°C are shown in Table 8, respectively.

[Comparative example 1]

Into a 3L detachable flask equipped with a stirring bar equipped with an oil bath, nitrogen gas was introduced, 1065g of NMP was added, and 248.3g of 3,3-(diaminodiphenyl)sulfone (specified as diamine 1) was added while stirring. , followed by adding 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic anhydride 1), and stirring at room temperature for 30 minutes. After heating up this to 50 degreeC and stirring for 12 hours, the oil bath was removed, it returned to room temperature, and the NMP solution (henceforth, also referred to as a varnish) of a transparent polyamic acid was obtained. Table 3 shows the composition and the weight average molecular weight (Mw) of the polyamic acid obtained therein. In addition, Table 6 shows the test results of the film cured at 350°C.

[Comparative examples 2 to 21]

In the same manner as in Comparative Example 1, the types of diamine 1 and tetracarboxylic anhydride 1 and their added masses were changed to those described in Table 3, respectively, and the same operation as in Comparative Example 1 was performed to obtain a varnish. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3, respectively. In addition, the test results of the films cured at 350°C are shown in Table 6, respectively.

[Comparative Example 22]

Into a 3L detachable flask with a stirring bar equipped with an oil bath, introduce nitrogen, add 1332g of NMP, add 299.8g of TFMB (specified as diamine 2) while stirring, add 294.2g of BPDA (specified as tetracarboxylic anhydride 1) , heated to 50°C and stirred for 12 hours. Into this, 105.6 g of both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400)) (specified as diamine containing a silicon group) was added to the The solution obtained by dissolving in 298g NMP was added dropwise using a dropping funnel. After completion of the dropwise addition, the temperature was raised to 80° C., and after stirring for 1 hour, the oil bath was removed and returned to room temperature to obtain a slightly cloudy NMP solution of opaque polyamic acid (hereinafter also referred to as varnish). Table 3 shows the composition and the weight average molecular weight (Mw) of the polyamic acid obtained therein. In addition, Table 6 shows the test results of the film cured at 350°C.

[Example 23]

Make 4.36g (0.02mol) pyromellitic anhydride (PMDA) and 25.78g BTDA in 240g N-methyl-2-pyrrolidone (NMP) disperse, will make 2.4gω-ω'-bis-(3-aminopropyl ) Polydimethylsiloxane (average molecular weight: 480) was dissolved in 50 g of diethylene glycol dimethyl ether (Dig), and a small amount of solution was gradually added dropwise, and stirred for 1 hour to allow them to react. In this way, after reacting diaminosiloxane and tetracarboxylic dianhydride, 14.62 g (0.05 mol) of 1,3-bis(4-aminophenoxy)benzene (TPE-R), and then further 11.17 g The 3,3-DAS was added gradually in small amounts in powder form.

[Example 24]

A 1-liter flask equipped with a stirring device, a dropping funnel, a thermometer, a condenser and a nitrogen displacement device was fixed in cold water. After the flask was replaced by nitrogen, mix 500g of dehydrated and purified N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 25.11g (0.0779 moles) of 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 15.48 g (0.0623 moles) of 3,3'-diaminodiphenylsulfone (3,3-DAS) and 14.96 g (0.0159 moles) of ω-ω'-bis-(3-amino Propyl) polydimethylsiloxane (molecular weight 960), according to conventional methods to obtain polyamic acid solution.

[Example 25]

2.87 g (25.1 mmol) of 1,4-diaminocyclohexane and 3.42 g (0.8 mmol) of Two-terminal amino-modified methyl phenyl silicone (X22-1660B-3). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added and stirred until uniform. Add 8.71 g (25.9 mmol) of diphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA) as a polycarboxylic acid derivative to the resulting solution at room temperature, and directly add Stirring was continued at the temperature for 24 hours to obtain a composition (polyamic acid solution).

[Example 26]

Add 7.85 g (24.5 mmol) of 4,4'-diamino-2,2'-bis(tri Fluoromethyl)biphenyl (hereinafter also referred to as "TFMB") and 2.03 g (1.6 mmol) of both-terminal amino-modified methylphenyl silicone (X22-9409). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added and stirred until uniform. Add 5.12 g (26.1 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as "CBDA") as component (A) to the resulting solution at room temperature, and directly Stirring was continued at this temperature for 24 hours to obtain a composition (polyamic acid solution).

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

[Table 7]

[Table 8]

The YI values and total light transmittances shown in Tables 4 to 6 and Table 8 represent the results (50ppm/100ppm/500ppm) when the oxygen concentrations in the oven were adjusted to 50ppm, 100ppm, and 500ppm, respectively.

As shown in Tables 4, 5, and 8, it was confirmed that Examples 1 to 66 simultaneously satisfied the following conditions in terms of film physical properties.

(1) The residual stress is below 25MPa

(2) The yellow index is below 7, which is less affected by the oxygen concentration

(3) The glass transition temperature in the temperature range above room temperature is 250°C or higher

(4) The total light transmittance is over 88%, less affected by oxygen concentration

(5) Tensile elongation over 30%

(6) NMP chemical resistance test for more than 30 minutes

(7) Even if the varnish is made of NMP alone, the thermally cured film will not become cloudy, so the total light transmittance is high

These satisfy the performance required for transparent substrates suitable for top-emission type flexible displays.

In Examples 1 to 33, 36, 37, 41, 42, 46, 47, and 53 to 66, the optical path difference Rth in the film thickness direction due to birefringence is 100 nm or less (20 to 90 nm), which is not only suitable for the top・The performance required for transparent substrates for light-emitting flexible displays also satisfies the performance required for use in transparent substrates for bottom-emission flexible displays and electrode substrates for touch panels. In addition, regarding the retardation Rth in the thickness direction, the polyimides (Comparative Examples 1 to 22) that do not use a silicon group-containing monomer as a comonomer and the polyimides that use a silicon group-containing monomer as a comonomer are compared. When comparing imides (Examples 1 to 33), the Rth of the polyimide using the silicon group-containing monomer is smaller, and it turns out that the silicon group-containing monomer contributes to lowering the Rth of the polyimide.

On the other hand, in Comparative Examples 1 to 26, the residual stress, chemical resistance, and tensile elongation were low, and the YI value and the total light transmittance deteriorated due to the influence of the oxygen concentration during curing.

From these results, it was confirmed that the resin obtained from the resin precursor of the present invention is colorless and transparent, has low residual stress with the inorganic film, and has excellent chemical resistance. , A resin film with little influence on the total light transmittance.

In addition, this invention is not limited to the said embodiment, It can change variously and can implement.

Industrial availability

The present invention can be suitably utilized in, for example, semiconductor insulating films, TFT-LCD insulating films, electrode protective films, production of flexible displays, and substrates for touch panel ITO electrodes, especially as substrates.

Claims (27)

1. a resin precursor, it is make to comprise polymeric composition that is amino and amino-reactive base to be polymerized the resin precursor obtained;

Described polymeric composition comprises the multivalent compounds being selected from the group of amino and amino-reactive base with more than 2;

Described multivalent compounds comprises containing silica-based compound;

Described multivalent compounds comprises the diamines represented with following formula (1);

Described resin precursor has the structure represented with following general formula (2),

In formula (2), there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, and h is the integer of 3 ~ 200;

The described amount containing silica-based compound counts 6 quality % ~ 25 quality % with the total mass benchmark of described multivalent compounds.

2. resin precursor according to claim 1, wherein, described amino-reactive base comprise select free carboxyl group, replace carboxyl and anhydride group composition group in more than one.

3. resin precursor according to claim 1 and 2, wherein, describedly comprises the silicoorganic compound represented with following general formula (3) containing silica-based compound,

In formula, there is multiple R ₂be the divalent organic group of singly-bound or carbon number 1 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, optionally there is multiple R ₅be the monovalent organic group of carbon number 1 ~ 20 independently of one another, L ₁, L ₂, and L ₃be amino, isocyanate group, carboxyl, anhydride group, perester radical, acid halide group, hydroxyl, epoxy group(ing) or sulfydryl independently of one another, j is the integer of 3 ~ 200, and k is the integer of 0 ~ 197.

4. resin precursor according to claim 3, wherein, in described general formula (3), L ₁and L ₂independently of one another for amino or anhydride group and k is 0.

5. resin precursor according to claim 4, wherein, in described general formula (3), L ₁and L ₂be amino.

6. the resin precursor according to any one of Claims 1 to 5, wherein, described resin precursor contains unit 1 and unit 2,

This unit 1 at least has the structure represented with following general formula (4):

In formula (4), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, optionally there is multiple X ₁be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and n is the integer of 1 ~ 100;

This unit 2 has the structure represented with following general formula (5) or the structure represented with following general formula (6), or has the structure represented with described general formula (5) and both the structures represented with described general formula (6),

In formula (5), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₂be bivalent aliphatic hydrocarbon or the O divalent aromatic base of carbon number 3 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, optionally there is multiple X ₂be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, l is the integer of 3 ~ 50, and m is the integer of 1 ~ 100;

In formula (6), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, there is multiple R ₈be trivalent aliphatic hydrocarbon or the trivalent aromatic base of carbon number 3 ~ 20 independently of one another, p is the integer of 1 ~ 100, and q is the integer of 3 ~ 50.

7. resin precursor according to claim 6, wherein, the total amount of described unit 1 and described unit 2 counts more than 30 quality % with the total mass benchmark of described resin precursor.

8. the resin precursor according to claim 6 or 7, wherein, described resin precursor is further containing the unit 3 with the structure represented with following general formula (7):

In formula, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, optionally there is multiple X ₃be the divalent organic group of carbon number 4 ~ 32 independently of one another, optionally there is multiple X ₄be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and t is the integer of 1 ~ 100.

9. resin precursor according to claim 8, wherein, in described general formula (7), X ₃to be structure be eliminates amino residue by 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl.

10. the resin precursor according to any one of claim 6 ~ 9, wherein, described unit 1 and described unit 2 comprise the position of more than a kind in the group being derived from and being selected from and being made up of pyromellitic acid anhydride (PMDA) and bibenzene tetracarboxylic dianhydride (BPDA) with the amount that the total amount benchmark at the acid dianhydride position being derived from described unit 1 and described unit 2 counts more than 60 % by mole and are selected from by 4 with being derived from, 4 '-oxydiphthalic acid dianhydride (ODPA), 4, 4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides (6FDA), hexanaphthene-1, 2, 4, 5-tetracarboxylic dianhydride (CHDA), 3, 3 ', 4, 4 '-diphenylsulfone acid dianhydride (DSDA), 4, 4 '-xenyl two (trimellitic acid monoester anhydride) (TAHQ) and 9, 9 '-bis-(3, 4-dicarboxyphenyi) position of more than one part combination in the group that forms of fluorenes dianhydride (BPAF).

11. resin precursors according to any one of claim 1 ~ 10, wherein, described R ₃with described R ₄be the univalent aliphatic series alkyl of carbon number 1 ~ 3 or the monovalence aromatic hydrocarbyl of carbon number 6 ~ 10 independently of one another.

12. resin precursors according to any one of claim 1 ~ 11, wherein, described R at least partially ₃with described R ₄for phenyl.

13. resin precursors according to any one of claim 1 ~ 12, wherein, described resin precursor is carried out being heating and curing with the condition of 300 ~ 500 DEG C under inert atmosphere and the resin obtained has at least one second-order transition temperature the scope of-150 DEG C ~ 0 DEG C and has at least one second-order transition temperature the scope of 150 DEG C ~ 380 DEG C, and be greater than 0 DEG C and the scope being less than 150 DEG C does not have second-order transition temperature.

14. resin precursors according to any one of claim 1 ~ 13, wherein, comprise the position being derived from bibenzene tetracarboxylic dianhydride (BPDA) of more than 20 % by mole in the total amount benchmark at the acid dianhydride position being derived from described resin precursor.

15. resin precursors according to any one of claim 1 ~ 14, wherein, the described resin precursor of part is by imidization.

16. 1 kinds of precursor mixtures, it comprises resin precursor according to any one of claim 1 ~ 15 and has the resin precursor of the structure represented with following general formula (8),

In formula, optionally there is multiple X ₃be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, and r is the integer of 1 ~ 100.

17. 1 kinds of flexible device materials, it comprises resin precursor according to any one of claim 1 ~ 15 or precursor mixture according to claim 16.

18. a resin film, its cured article of resin precursor according to any one of claim 1 ~ 15 or the cured article of precursor mixture according to claim 16.

19. a resin combination, it contains resin precursor according to any one of claim 1 ~ 15 or precursor mixture according to claim 16 and solvent.

20. resin combinations according to claim 19, wherein, the yellowness index of the resin obtained as follows under 20 μm of thickness is shown as less than 7, described resin is launch described resin combination on the surface of supporter after, is obtained by the described resin precursor imidization comprised by being carried out heating with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by described resin combination in described resin combination.

21. resin combinations according to claim 19 or 20, wherein, the unrelieved stress of the resin obtained as follows under 10 μm of thickness is shown as below 25MPa, described resin is launch described resin combination on the surface of supporter after, is obtained by the described resin precursor imidization comprised by being carried out heating with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by described resin combination in described resin combination.

22. 1 kinds of resin films, the cured article of its resin combination according to any one of claim 19 ~ 21.

The manufacture method of 23. 1 kinds of resin films, it comprises:

The surface of supporter is launched the operation of the resin combination according to any one of claim 19 ~ 21;

Heat described supporter and described resin combination and by the described resin precursor imidization comprised in described resin combination to form the operation of resin film; And

By the operation that described resin film is peeled off from described supporter.

24. 1 kinds of layered products, its resin molding comprising supporter and formed on the surface of described supporter, the cured article of the resin combination of described resin molding according to any one of claim 19 ~ 21.

The manufacture method of 25. 1 kinds of layered products, it comprises:

The surface of supporter is launched the operation of the resin combination according to any one of claim 19 ~ 21; And

Heat described supporter and described resin combination and by the described resin precursor imidization comprised in described resin combination to form resin molding, obtain the operation of the layered product comprising described supporter and described resin molding thus.

26. 1 kinds of polyimide resin films, it is the polyimide resin film used in the manufacture of display base plate, and the Rth when thickness 20 μm is 20 ~ 90nm.

The manufacture method of 27. 1 kinds of display base plates, it comprises:

The surface of supporter is launched the operation comprising the resin combination of polyimide precursor;

Heat described supporter and described resin combination and by polyimide precursor imidization to form the operation of polyimide resin film according to claim 26;

The operation of forming element on described polyimide resin film; And

By the operation that the described polyimide resin film defining described element is peeled off from described supporter.