KR20170097243A - Resin precursor, resin composition containing said resin precursor, resin film, method for producing said resin film, laminate, and method for producing said laminate - Google Patents

Abstract

로 나타내는 디아민을 포함하고, 그 수지 전구체가 하기 일반식 (2)：

로 나타내는 구조를 갖고, 그 규소기 함유 화합물의 양이 그 다가 화합물의 총질량 기준으로 6 질량％ ∼ 25 질량％ 인 수지 전구체.It is possible to provide a transparent resin cured product without requiring a special combination of solvents and to provide a cured product which has a low residual stress generated between itself and an inorganic film and is excellent in chemical resistance, And a resin precursor capable of imparting a resin cured product having a small influence on the total light transmittance.
A resin precursor obtained by polymerizing a polymerization component comprising an amino group and an amino group reactive group, wherein the polymerization component comprises a polyvalent compound having two or more groups selected from an amino group and an amino group reactive group, and the polyvalent compound includes a silicon group- (1): " (1) "

, And the resin precursor is represented by the following general formula (2):

, And the amount of the silicon group-containing compound is 6% by mass to 25% by mass based on the total mass of the compound.

Description

Technical Field The present invention relates to a resin precursor and a resin composition containing the resin precursor, a resin film, a process for producing the same, a laminate, and a process for producing the same. TECHNICAL FIELD [0001] The present invention relates to a resin precursor, PRODUCING SAID LAMINATE}

The present invention relates to, for example, a resin precursor used in a substrate for a flexible device, a resin composition containing the resin precursor, a resin film, a production method thereof, a laminate, and a production method thereof.

In general, for applications requiring high heat resistance, a polyimide (PI) resin film is used as the resin film. A general polyimide resin is obtained by subjecting an aromatic dianhydride and an aromatic diamine to solution polymerization to prepare a polyimide precursor, followed by ring-closing dehydration at a high temperature, thermal imidization, or chemical imidization using a catalyst It is a heat-resistant resin.

The polyimide resin is an insoluble and refractory super heat resistant resin and has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, the polyimide resin is used in a wide range of fields including insulating coatings, insulating films, semiconductors, and electronic materials such as electrode protective films of TFT-LCDs. In recent years, polyimide resins have been widely used in the field of display materials such as liquid crystal alignment films Instead, adoption of a colorless transparent flexible substrate using lightness and flexibility has been studied.

However, a general polyimide resin is colored in brown or yellow by a high directional ring density, has a low transmittance in the visible light region, and is difficult to be used in fields requiring transparency.

With respect to the problem of improving the transparency of such a polyimide, for example, Non-Patent Document 1 discloses a polyimide having improved transparency and color transparency by using acid dianhydride having a specific structure and diamine having a specific structure, Mead is described. In the patent documents 1 to 4, 4,4-bis (diaminodiphenyl) sulfone (hereinafter also referred to as 4,4-DAS) or 3,3-bis (diaminodiphenyl) sulfone , 3-DAS) and an acid dianhydride having a specific structure, transparency and color transparency are improved.

In Examples 9 and 10 of the following Patent Literature 6, a specific aromatic tetracarboxylic acid dianhydride, an alicyclic diamine, and a silicon-containing diamine are copolymerized to produce a polyimide exhibiting high Tg, transparency, high adhesion, Polyimide precursors which are capable of producing polyimide precursors.

In Examples 3 and 4 of the following patent documents 7 and 8, a polyimide precursor obtained by copolymerizing an aromatic tetracarboxylic acid dianhydride, bis (diaminodiphenyl) sulfone and a silicon-containing diamine was used as a semiconductor A protective resin, and a photosensitive resin composition.

Japanese Patent Application Laid-Open No. 61-141732 Japanese Patent Application Laid-Open No. 06-271670 Japanese Laid-Open Patent Publication No. 09-040774 Japanese Patent Application Laid-Open No. 2000-313804 International publication number 2012/118020 pamphlet International publication number 2011/122198 pamphlet International Publication No. 1991/010699 pamphlet Japanese Patent Application Laid-Open No. 4-224823

 The latest polyimide (foundation and application), Japan Polyimide Research Association, P152

However, the physical properties of the known transparent polyimide are not sufficient for use as, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protecting film, an ITO electrode substrate for a touch panel, and a heat-resistant colorless transparent substrate for a flexible display.

For example, when a polyimide resin is used for a colorless transparent substrate for a flexible display, a polyimide film is formed on a support glass (hereinafter also referred to as a support), and on the polyimide film, , And an inorganic film may be formed. When the coefficient of linear expansion of the polyimide (hereinafter also referred to as CTE) is high, residual stress is generated between the polyimide film and the inorganic film due to CTE mismatch between the inorganic film or the support glass and the polyimide film, There is a problem that the support glass is bent or the performance of the TFT element is lowered. Therefore, there is a problem that the residual stress of the polyimide is lowered in order to improve the warpage of the support glass. The polyimide described in Patent Documents 1 to 4 has a high residual stress and has a problem that the support glass is warped when it is applied to a colorless transparent substrate for a flexible display.

In order to produce the polyimide film, for example, a polyimide precursor is coated on a glass substrate, the glass substrate coated with the polyimide precursor is introduced into an oven into which nitrogen gas is introduced, (Hereinafter, also referred to as a curing process) is generally required. In the polyimide having improved transmittance, hue and transparency described in Patent Documents 1 to 4 and Non-Patent Document 1, when the oxygen concentration in the oven furnace during curing is high, specifically when the oxygen concentration is 100 ppm or more, YI And the total light transmittance is lowered.

When a polyimide resin is used for a colorless transparent substrate for a flexible display, a TFT element is usually formed on the polyimide film by a photolithography process using a photoresist. A polyimide film (hereinafter, also referred to as a polyimide substrate) used for a colorless transparent substrate for a flexible display is exposed to a chemical such as a photoresist stripping liquid used in the step of stripping the photoresist included in this process , It is necessary to have chemical resistance to these medicines. In the case of polyimide comprising 4,4-DAS or 3,3-DAS and acid dianhydride having a specific structure as described in Patent Document 1, the polyimide substrate has a small crack There is a problem that the polyimide substrate is opaque and the total light transmittance is lowered.

Patent Document 5 describes that flexible silicon-containing diamines are introduced by block copolymerization for the purpose of reducing residual stress while maintaining the glass transition temperature or Young's modulus of polyimide. However, as described in Comparative Example 4 of Patent Document 5, when the silicon-containing diamine is copolymerized with the block, the phase separation of the silicon portion progresses and the refractive index becomes lower than that of the polyimide precursor unless the polyimide precursor is dissolved by using a combination of special solvents In a different sea (island) structure, the structure of the island portion becomes larger, so that the film becomes opaque and the total light transmittance is lowered. When a combination of a special solvent having a low boiling point is used, if a polyimide precursor solution is applied to a substrate and then left at room temperature for several hours, haze may occur and the coating film may become cloudy, . In order to produce a transparent thermosetting film by polyimide obtained by block copolymerization of a silicon-containing diamine as described above, there is a problem in that it is necessary to dissolve the precursor by using a combination of special solvents and to control the time after which the precursor solution is applied there was.

In Examples 9 and 10 of Patent Document 6, a polyimide precursor obtained by copolymerizing an aromatic tetracarboxylic acid dianhydride, an alicyclic diamine and silicon diamine, and a polyimide obtained therefrom are described. However, the inventors of the present invention have found that the polyamide has a high yellowing degree, a low total light transmittance, and a yellowing degree and a transmittance which are easily affected by the oxygen concentration at the time of polyimide curing See Example 25).

Patent Documents 7 and 8 disclose a polyimide precursor obtained by copolymerizing (diaminodiphenyl) sulfone, an aromatic tetracarboxylic acid dianhydride, and silicone diamine, and a polyimide obtained therefrom. However, the inventors of the present invention have found that the mass ratio of the silicon-containing monomer to the total mass of the silicon-containing monomer, polyvalent hydrocarbon derivative, and diamine compound used in synthesizing the polyimide precursor, Therefore, there is a problem in that the obtained polyimide is cloudy and is not suitable for use in a transparent display because the residual stress of the obtained polyimide is large, which is inadequate in the process of the display and on the other hand in Patent Document 8 23, 24).

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and it is an object of the present invention to provide a transparent resin cured product which can provide a transparent resin cured product without requiring a special combination of solvents, And which can give a resin cured product excellent in YI value due to oxygen concentration at the time of curing process and having little influence on the total light transmittance. Another object of the present invention is to provide a resin composition containing the resin precursor, a resin film obtained by curing the resin composition, a process for producing the resin film, a laminate and a process for producing the same.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that a heat-resistant resin precursor having a specific structure can form a transparent resin cured product without requiring a special combination of solvents, It has been found out that the cargo is a resin hardened product having a low residual stress generated between the inorganic film and the chemical resistance and having little influence on the YI value or the total light transmittance due to the oxygen concentration in the curing process, The present invention has been accomplished on the basis of these findings. That is, the present invention is as follows.

[1] A resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino group-

Wherein the polymerization component comprises a polyfunctional compound having two or more groups selected from an amino group and an amino group reactive group,

Wherein the compound comprises a silicon-containing compound,

Wherein the compound is a compound represented by the following formula (1):

[Chemical Formula 1]

, ≪ / RTI >

Wherein the resin precursor is represented by the following general formula (2):

(2)

(Wherein, in the formulas, R ₃ and R ₄ , which are plural, are each independently a monovalent organic group having 1 to 20 carbon atoms and h is an integer of 3 to 200)

Wherein the amount of the silicon-containing compound is from 6% by mass to 25% by mass based on the total mass of the compound

The resin precursor.

[2] The resin precursor according to [1], wherein the amino group-reactive group comprises at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group and an acid anhydride group.

[3] The silicon-containing compound according to [

(3)

Wherein the plurality of R _{2 s} present in plural are independently a single bond or a divalent organic group having 1 to 20 carbon atoms and R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms a plurality to be R ₅ are, to be present, each independently, a monovalent organic group having a carbon number of 1 ~ 20, L _1, L _2, and L ₃ are, each independently, an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, (1), wherein the silicon compound represented by the general formula (1) is an acid ester group, an acid halide group, a hydroxyl group, an epoxy group, or a mercapto group, j is an integer of 3 to 200, Or the resin precursor according to [2].

[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 together are an amino group.

[6] The resin precursor contains unit 1 and unit 2,

Wherein the unit 1 is represented by at least the following general formula (4);

[Chemical Formula 4]

(Wherein R _{1 s} present in plural numbers are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and X _{1, which} may be present in plural numbers, 32, and n is an integer of 1 to 100.}

, ≪ / RTI >

And the unit 2 is represented by the following general formula (5):

[Chemical Formula 5]

Wherein the plurality of R _{1 s} present are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and the plurality of R _{2 s} present may be independently selected from the group consisting of 3 to 20 carbon atoms And R < ₃ > and R < ₄ > are each independently a monovalent organic group having 1 to 20 carbon atoms, and the plurality of X _{2, which} may be present, (1), wherein m is an integer of 1 to 100, or a structure represented by the following general formula (6):

[Chemical Formula 6]

(Wherein R _{1 s} present in plural are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and R ₃ and R ₄ , which are present in plural numbers, A plurality of R _{8 s} are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a trivalent aromatic group, p is an integer of 1 to 100, and q is (1) to (5), which has both of a structure represented by the general formula (5) and a structure represented by the general formula (6) Resin precursor.

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

[8] The resin precursor is represented by the following general formula (7):

(7)

(Wherein R _{1 s} present in plural numbers are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and X _{3, which} may be present in plural numbers, And a plurality of X _{4 which} may be present are each independently a tetravalent organic group having 4 to 32 carbon atoms and t is an integer of 1 to 100. The unit 3 having the structure represented by The resin precursor according to [6] or [7], further comprising:

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

[10] The unit 1 and the unit 2

A moiety derived from at least one selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic acid dianhydride (BPDA)

4,4'-oxydiphthalic dianhydride (ODPA), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid 2 (CHDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), 4,4'-biphenylbis (trimellitic acid monoester acid anhydride) (TAHQ), and (9), 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF)

, The resin precursor according to any one of [6] to [9], wherein the unit is a combination of the unit 1 and the acid anhydride-derived site of the unit 2 in an amount of 60 mol% or more based on the total amount.

[11] The compound according to any one of [1] to [10], wherein R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. ≪ / RTI >

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

[13] The resin obtained by heat-curing the resin precursor under an inert atmosphere at 300 to 500 ° C has a glass transition temperature of at least one of -150 ° C to 0 ° C and at least one of 150 ° C to 380 ° C The resin precursor according to any one of [1] to [12], which has a glass transition temperature and does not have a glass transition temperature in a region larger than 0 ° C and smaller than 150 ° C.

[14] The resin composition according to any one of [1] to [13], wherein the portion derived from biphenyltetracarboxylic acid dianhydride (BPDA) comprises 20 mol% or more based on the total amount of the acid anhydride- The resin precursor described.

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

[16] A resin composition comprising the resin precursor according to any one of [1] to [15] and a resin precursor represented by the following general formula (8):

[Chemical Formula 8]

(Wherein X _{3, which} may be plural, may be independently a quaternary organic group having 4 to 32 carbon atoms, and plural R _{1 s} may independently be a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms , Or a monovalent aromatic group, and r is an integer of 1 to 100. A precursor mixture comprising a resin precursor having a structure represented by formula

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

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

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

[20] The resin composition is developed on the surface of a support, and then the resin composition is heated at 300 ° C. to 500 ° C. in a nitrogen atmosphere to imidize the resin precursor contained in the resin composition. A 20 μm film The resin composition according to [19], wherein the yellowness in thickness is 7 or less.

[21] The resin composition is developed on the surface of a support, and then the resin composition is heated at 300 ° C. to 500 ° C. in a nitrogen atmosphere to imidize the resin precursor contained in the resin composition to form a 10 μm film The resin composition according to [19] or [20], wherein the residual stress at the thickness is 25 MPa or less.

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

[23] A method for producing a resin composition, which comprises the steps of developing the resin composition according to any one of [19] to [21]

Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film,

A step of peeling the resin film from the support

Wherein the resin film comprises a resin.

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

[25] A method for producing a resin composition, comprising the steps of: developing a resin composition according to any one of [19] to [21]

Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film and thereby obtaining a laminate comprising the support and the resin film

And a step of forming the laminate.

[26] A polyimide resin film used for manufacturing a display substrate, wherein the polyimide resin film has an Rth of 20 to 90 nm at a thickness of 20 μm.

[27] A method for producing a polyimide precursor, comprising the steps of: developing a resin composition comprising a polyimide precursor on a surface of a 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 step of forming an element on the polyimide resin film,

A step of peeling the polyimide resin film on which the element is formed from the support

Wherein the display substrate has a first surface and a second surface.

INDUSTRIAL APPLICABILITY The present invention can provide a transparent resin cured product without requiring a special combination of solvents, and also has a low residual stress generated between the inorganic cured film and the inorganic film, has excellent chemical resistance, There is provided a resin precursor capable of imparting a resin cured product having a small influence on YI value and total light transmittance by oxygen concentration.

Hereinafter, exemplary embodiments of the present invention (hereinafter abbreviated as " embodiments ") will be described in detail. The present invention is not limited to the following embodiments, and various modifications may be made within the scope of the present invention. Unless otherwise specified, the number of repeating structural units in the formula of the present disclosure is merely intended to include the number of structural units in the resin precursor as a whole, and therefore, It should be noted that it is not done. Unless otherwise specified, the characteristic values described in this disclosure are intended to be values measured by the method described in the section of [Examples], or equivalents thereof, by methods understood by those skilled in the art.

<Resin Precursor>

The resin precursor according to the embodiment of the present invention,

As a resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino group reactive group,

Wherein the polymerization component comprises a polyfunctional compound having two or more groups selected from an amino group and an amino group reactive group,

Wherein the compound comprises a silicon-containing compound,

Wherein the compound is a compound represented by the following formula (1):

[Chemical Formula 9]

, &Lt; / RTI &gt;

Wherein the resin precursor is represented by the following general formula (2):

[Chemical formula 10]

(Wherein, in the formulas, R ₃ and R ₄ , which are plural, are each independently a monovalent organic group having 1 to 20 carbon atoms and h is an integer of 3 to 200)

Wherein the amount of the silicon-containing compound is from 6% by mass to 25% by mass based on the total mass of the compound

Thereby providing the resin precursor.

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

In the present disclosure, an amino group reactive group is intended to mean a group having reactivity to an amino group. Examples of the amino group-reactive group include groups having an acid group (e.g., a carboxyl group, an acid anhydride group, and a substituted carboxyl group (e.g., an acid ester group, an acid halide group, etc.), a hydroxyl group, Pottery can be heard. Examples of the acid group-containing compound include dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, and acid anhydrides, acid esters and acid chlorides of these carboxylic acids . Therefore, the resin precursor of the present embodiment may be a polyimide precursor. In a typical embodiment, the amino group-reactive group includes at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group. In a preferred embodiment, the amino group-reactive group is at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group and an acid anhydride group.

The polyfunctional compound includes at least a diamine represented by the general formula (1). Examples of the compound represented by the general formula (1) include 4,4- (diaminodiphenyl) sulfone (hereinafter also referred to as 4,4-DAS), 3,4- (diaminodiphenyl) 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 compound containing a silicon group. The amount of the silicon group-containing compound is 6% by mass to 25% by mass (hereinafter, this mass fraction is also referred to as the silicon group-containing monomer concentration), based on the mass of the polyvalent compound. The concentration of the silicon group-containing monomer is advantageously 6 mass% or more from the viewpoint of sufficiently obtaining the effect of lowering the stress generated in the resin film and the inorganic film and the effect of lowering the yellowness, and is preferably 7 mass% or more, more preferably 8 mass% , And more preferably 10 mass% or more. On the other hand, when the concentration of the silicon group-containing monomer is 25 mass% or less, the polyimide obtained is advantageous from the standpoint of improvement in transparency, lowering of yellow color and good heat resistance without clouding, and preferably 22 mass% And more preferably 20 mass% or less. It is particularly preferable that the concentration of the silicon group-containing monomer is 10% by mass or more and 20% by mass or less from the viewpoint of satisfactory chemical resistance, YI value, total light transmittance, birefringence, residual stress and oxygen dependence of optical properties.

In the general formula (2), plural R ₃ and R _{4 which} are present are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbon atoms include a monovalent hydrocarbon group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an epoxy group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoints of heat resistance and residual stress. Specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t -Butyl group, pentyl group, hexyl group and the like. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms from the viewpoint of the above, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms from the viewpoint of the above, and specific examples thereof include a phenyl group, a tolyl group and a naphthyl group.

Examples of the amino group having 1 to 20 carbon atoms include amino group, substituted amino group (e.g., bis (trialkylsilyl) amino group), and the like.

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

In the general formula (2), the plurality of R ₃ and R _{4 which} are present are each independently a monovalent aliphatic hydrocarbon group of 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms. The obtained polyimide membrane And is preferable from the viewpoint of having high heat resistance and low residual stress. From this viewpoint, 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 to 200, preferably an integer of 10 to 200, more preferably an integer of 20 to 150, still more preferably an integer of 30 to 100, Lt; / RTI &gt; When h is 2 or less, the residual stress of the polyimide obtained from the resin precursor of the present disclosure may deteriorate (i.e., increase). When h exceeds 200, when a varnish containing a resin precursor and a solvent is prepared, The varnish may be opaque or the mechanical strength of the polyimide may be lowered.

In the resin precursor of the present embodiment, it is preferable that the silicon group-containing compound is a compound represented by the following general formula (3):

(11)

Wherein the plurality of R _{2 s} present in plural are independently a single bond or a divalent organic group having 1 to 20 carbon atoms and R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms a plurality to be R ₅ are, to be present, each independently, a monovalent organic group having a carbon number of 1 ~ 20, L _1, L _2, and L ₃ are, each independently, an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, An acid ester group, an acid halide group, a hydroxyl group, an epoxy group, or a mercapto group, j is an integer of 3 to 200, and k is an integer of 0 to 197). In a preferred embodiment, the silicon group-containing compound is a silicone compound represented by the general formula (3).

Examples of the divalent organic group having 1 to 20 carbon atoms in R ₂ include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms. The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms in terms of heat resistance, residual stress and cost, and is preferably an alkylene group having from 2 to 10 carbon atoms such as a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, And the like. The cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms in view of the above, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group. Among them, a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms is preferable from the above viewpoint. As the arylene group having 6 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms is preferable in view of the above, and phenylene group, naphthylene group and the like can be given.

In the formula (3), R ₃ and R ₄ are the same meanings as R ₃ and R ₄ in general formula (2), preferred embodiments are as defined above for formula (2). R ₅ is the same as a monovalent organic group having 1 to 20 carbon atoms, that is, R ₃ and R _4, and preferred embodiments thereof are the same as R ₃ and R ₄ .

In the general formula (3), L ₁ , L ₂ and L ₃ each independently represents an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, an acid halide group, a hydroxyl group, Lt; / RTI &gt;

The amino group may be substituted, and examples thereof include a bis (trialkylsilyl) amino group and the like. Specific examples of the compound represented by the general formula (3) in which L ₁ , L ₂ and L ₃ are amino groups include amino-modified methylphenyl silicone at both terminals (for example, X22-1660B-3 Terminal number of amino-modified dimethylsilicone (for example, X22-161A (number average molecular weight 1,600), X22-161B (number average molecular weight 3,000) manufactured by Shin-Etsu Chemical Co., BY16-835U (number average molecular weight: 900) manufactured by Toray Dow Corning; and Saira Plain FM3311 (number average molecular weight: 1,000) manufactured by Chisso Corporation) and KF8012 (number average molecular weight: 4,400).

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are isocyanate groups include isocyanate-modified silicon obtained by reacting the above-described amino-terminal modified silicone with a phosgene compound.

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

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are acid anhydride groups include compounds represented by the following formulas:

[Chemical Formula 12]

And an acyl compound having at least one of the groups represented by R &lt; 1 &gt;

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

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are acid ester groups include compounds obtained by reacting an alcohol with a compound in which L ₁ , L ₂ , and L ₃ are a carboxyl group or an acid anhydride group.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are acid halide groups include a carboxylic acid chloride, a carboxylic acid fluoride, a carboxylic acid bromide, and a carboxylic acid iodide.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are hydroxyl groups include KF-6000 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), KF- 6002 (manufactured by Shin-Etsu Chemical Co., number average molecular weight: 3,200) and KF-6003 (manufactured by Shin-Etsu Chemical Co., number average molecular weight: 5,000). The compound having a hydroxy group is considered to react with a compound having a carboxyl group or an acid anhydride group.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are epoxy groups include X22-163 (Shin-Etsu Chemical Co., Ltd., number average molecular weight: 400) and KF-105 980), X22-163A (number average molecular weight 2,000), X22-163B (Shin-Etsu Chemical Co., number average molecular weight 3,500), X22-163C (Shin-Etsu Chemical Co., number average molecular weight 5,400), both end alicyclic epoxy X22-9002 (manufactured by Shin-Etsu Chemical Co., Ltd., having a number average molecular weight of 1,000), X22-169B (number average molecular weight of 3,400 manufactured by Shin-Etsu Chemical Co., Ltd.) g / mol); and the like. A compound having an epoxy group is considered to react with a diamine.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are mercapto groups include X22-167B (Shin-Etsu Chemical Co., number average molecular weight: 3,400), X22-167C . The compound having a mercapto group is considered to react with a compound having a carboxyl group or an acid anhydride group.

It is preferable that L ₁ , L ₂ and L ₃ are each independently an amino group or an acid anhydride group from the viewpoints of improving the molecular weight of the resin precursor or from the viewpoint of the heat resistance of the obtained polyimide, From the standpoint of avoiding the opacity of the varnish, or from the viewpoint of cost, each independently is preferably an amino group.

Alternatively, it is preferable that L ₁ and L ₂ each independently represent an amino group or an acid anhydride group, and k is 0, from the viewpoint of the opacity avoidance of the resin precursor and the varnish containing the solvent, or from the viewpoint of cost. In this case, it is more preferable that L ₁ and L ₂ together are an amino group.

In the general formula (3), a preferable embodiment of j is the same as that described above for h in the general formula (2). In the general formula (3), k is an integer of 0 to 197, preferably 0 to 100, more preferably 0 to 50, and particularly preferably 0 to 25. When k is more than 197, when the varnish containing the resin precursor and the solvent is prepared, the varnish sometimes becomes opaque. When k is 0, it is preferable from the viewpoint of the improvement of the molecular weight of the resin precursor or the heat resistance of the obtained polyimide. When k is 0, it is advantageous that j is 3 to 200 from the viewpoints of improving the molecular weight of the resin precursor or the heat resistance of the obtained polyimide.

In a preferred embodiment, in the formulas of the present disclosure, R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group of 1 to 3 carbon atoms, or a monovalent aliphatic hydrocarbon group of 6 to 10 carbon atoms in terms of residual stress and cost. Lt; / RTI &gt; aromatic hydrocarbon group. Alternatively, in each formula of the present disclosure, it is preferable that a part of R ₃ and R ₄ is a phenyl group in view of heat resistance and residual stress.

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

&Lt; Tetracarboxylic acid dianhydride &gt;

Examples of the tetracarboxylic acid dianhydride as an example of the polyvalent compound contained in the polymerization raw material include concretely aromatic tetracarboxylic acid dianhydride having 8 to 36 carbon atoms and alicyclic tetracarboxylic acid having 6 to 36 carbon atoms 2-anhydride are preferable from the viewpoint of reduction of YI value and total light transmittance.

More specifically, there can be mentioned 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- (2,5-dioxotetrahydro-3-furanyl) -3- Methyl-cyclohexene-1,2-dicarboxylic acid anhydride, pyromellitic acid dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3 ', 4 , 4'-benzophenonetetracarboxylic acid dianhydride (hereinafter also referred to as BTDA), 2,2 ', 3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic acid dianhydride (hereinafter also referred to as BPDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (hereinafter also referred to as DSDA), 2,2' 3,3'-biphenyltetracarboxylic acid dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2- Dicarboxylic dianhydride, 4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene- Di-phthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenoxy) (3, 4-dicarboxyphenoxy) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) Phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter also referred to as BPADA), bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,6- 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-te Naphthalenetetracarboxylic dianhydride, 1,4-naphthalenetetracarboxylic acid dianhydride, 1,2,4,6-naphthalenetetracarboxylic dianhydride, 1,2,4,6-naphthalenetetracarboxylic dianhydride, Anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, Tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (hereinafter also referred to as CBDA) ), Cyclopentanetetracarboxylic acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride (hereinafter referred to as &quot; , CHDA), 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) 2 Anhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2- (Cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicar (Cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylate [1S, 5R, 6R] -3-oxabicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, [3,2,1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione), 4- (2,5-dioxotetrahydrofuran- -1,4-dicarboxylic acid anhydride, ethylene glycol-bis- (3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'- Biphenylbis (trimellitic acid monoester acid anhydride) (hereinafter also referred to as TAHQ), 9,9'-bis (3,4-dicarboxyphenyl) Lu fluorene (also referred to below, BPAF.) 2 anhydride, and the like.

Among them, BTDA and PMDA are preferable from the viewpoint of reduction of CTE, improvement of chemical resistance, improvement of glass transition temperature (Tg) and improvement of machine elongation. Further, 6FDA, ODPA and BPADA are preferable from the viewpoints of reduction in yellowness, reduction in birefringence and improvement in machine elongation. Further, BPDA is preferable from the viewpoints of reduction of residual stress, lowering of yellowness, lowering of birefringence, improvement of chemical resistance, improvement of Tg and improvement of machine elongation. CHDA is also preferable from the viewpoints of reduction of residual stress and reduction of yellowing degree. Of these, BPDA having a rigid structure that exhibits high internal chemical resistance, high Tg and low CTE and tetracarboxylic acid dianhydride selected from the group consisting of 6FDA, ODPA, and CHDA having low yellowness and low birefringence are used in combination Is preferable from the viewpoints of the intrinsic chemical resistance, the lowering of the residual stress, the lowering of the yellow color, the lowering of the birefringence, and the improvement of the total light transmittance.

In particular, from the viewpoint of high durability, chemical resistance, and high Young's modulus, the BPDA-derived moiety is preferably 20 mol% or more, more preferably 50 mol% or more of the moiety derived from the entire acid dianhydride , More preferably 80 mol% or more, and may be 100%.

<Dicarboxylic acid>

In addition to the above-mentioned tetracarboxylic acid dianhydride, the resin precursor in the present embodiment can be added to the resin precursor in the range of not deteriorating the performance, such as improvement of the machine elongation, improvement of the glass transition temperature, For the purpose of adjusting the performance, the thermosetting film may be made into a polyamideimide by introducing a polyamide component by copolymerizing a dicarboxylic acid. Examples of such dicarboxylic acids include dicarboxylic acids having aromatic rings and alicyclic dicarboxylic acids. In particular, from the viewpoint of reduction in YI value and total light transmittance, aromatic dicarboxylic acids having 8 to 36 carbon atoms At least one compound selected from the group consisting of dicarboxylic acids and alicyclic dicarboxylic acids having 6 to 34 carbon atoms is preferable. Specific examples thereof include 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'- Oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4-hydroxyphenyl) benzoic acid, Carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'- Phenyl dicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) 4,4'-bis (3-carboxyphenoxy) phenyl) fluorene, 4,4'-bis (4-carboxyphenoxy) '-Bis (4-carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenyl Biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3-carboxyphenoxy) biphenyl, 4,4'- (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) (4-carboxyphenoxy) -m-terphenyl, 3,4'-bis (4-carboxyphenoxy) , 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3-carboxyphenoxy) (3-carboxyphenoxy) -p-terphenyl, 3,4'-bis (3-carboxyphenoxy) -m- terphenyl, 3,3 ' 4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 4-cyclohexanedicarboxylic acid, 4-cyclohexane dicarboxylic acid, Phenylene diacetic acid, 1,4-phenylene dicarboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, and 5-aminoisoproxenes described in WO 2005/068535 pamphlet And deoxidation derivatives. When these dicarboxylic acids are actually copolymerized with the polymer, they may be used in the form of an acid chloride derivative or an active ester derivative derived from thionyl chloride or the like.

Among them, terephthalic acid is particularly preferable from the viewpoint of reduction of YI value and improvement of Tg. When dicarboxylic acid is used instead of tetracarboxylic acid, it is preferable from the viewpoint of chemical resistance that the dicarboxylic acid is 50 mol% or less with respect to the total number of moles of dicarboxylic acid and tetracarboxylic acid.

<Diamine>

The diamine contained in the polymerization component includes a diamine represented by the general formula (1). The diamine represented by the general formula (1) can constitute, for example, a diamine-derived site of the unit 1 described later. In the resin precursor, a site derived from a diamine represented by the general formula (1) is preferably a site derived from a diamine in which the polyimide film has a suitable yellowness, a low birefringence, an improvement in the total light transmittance, a decrease in residual stress generated between the film and the inorganic film, From the viewpoint of obtaining Tg and high strength, it is preferably 20 mol% or more, more preferably 50 mol% or more, and even more preferably 80 mol% or more of the entire diamine-derived site.

The diamine may include a diamine having a divalent silicon-containing group having 2 to 100 silicon atoms (hereinafter, also simply referred to as a silicon-containing diamine). As the silicon-containing diamine, for example, the following general formula (9):

[Chemical Formula 13]

Wherein the plurality of R _{2 s} present are independently a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a divalent aromatic group and each of R ₃ and R ₄ is independently a monovalent C 1-20 (L) is an integer of 3 to 50, is suitable as the diamino (poly) siloxane. Such a diamine can constitute, for example, a unit 2 to be described later.

Examples of preferred structures of R ₂ in the general formula (9) include a methylene group, an ethylene group, a propylene group, a butylene group and a phenylene group. Suitable examples of R ₃ and R ₄ in the general formula (9) include a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, and particularly preferably at least a part of them is a phenyl group.

Specific examples of the compound represented by the above general formula (9) include a methylphenyl silicone oil modified at both ends (X22-1660B-3 (number average molecular weight: 4400) and X22-9409 (number average molecular weight: 1300) (Number average molecular weight: 3,000), KF8021 (number average molecular weight: 4400) manufactured by Toray Dow Corning Co., Ltd., BY16-835U (number average molecular weight: 1,600) Average molecular weight: 900) manufactured by Chisso Corporation: Sira Plain FM3311 (number average molecular weight: 1000)). Of these, both terminal amine-modified methylphenyl silicone oils are particularly preferred from the viewpoints of chemical resistance improvement and Tg improvement.

Further, the diamine may be 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'-) diaminodiphenylsulfone, 4,4'- (or 3,3'-) diaminodiphenylsulfide, 4,4 ' (4-aminophenoxy) phenylsulfone, 4,4'-di (3-aminophenoxy) phenylsulfone, 4,4'- Bis (4-aminophenoxy) benzene, 2,2-bis {4- (4-aminophenoxy) benzene, -Aminophenoxy) phenyl} propane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,2'-bis , 6,6'-tetramethyl-4,4'-diaminobiphenyl, 2,2 ', 6,6'-tetratrifluoromethyl-4,4'-diaminobiphenyl, bis {(4 (4-aminophenyl) fluorene, 9,9-bis (4-aminophenoxyphenyl) fluorene, Dimethylbenzidine , 3,3'-dimethoxybenzidine and 3,5-diaminobenzoic acid, etc., 2,6-diaminopyridine, 2,4-diaminopyridine, bis (4-aminophenyl- -Benzene, 3,3'-bis (trifluoromethyl) -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'- At least one selected from the group consisting of hexafluoropropane (3,3'-6F) and 2,2'-bis (4-aminophenyl) hexafluoropropane (4,4'-6F) You can. These diamines can constitute a diamine-derived site of the unit 3 described later. Of these, 1,4-cyclohexanediamine and TFMB are most preferable from the viewpoints of reduction in yellowness, reduction in CTE and reduction in YI value.

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

Unit 1 comprises at least the following general formula (4);

[Chemical Formula 14]

(Wherein R _{1 s} present in plural numbers are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and X _{1, which} may be present in plural numbers, 32, and n is an integer of 1 to 100.}

, &Lt; / RTI &gt;

The unit 2 is represented by the following general formula (5):

[Chemical Formula 15]

Wherein the plurality of R _{1 s} present are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and the plurality of R _{2 s} present may be independently selected from the group consisting of 3 to 20 carbon atoms And R &lt; ₃ &gt; and R &lt; ₄ &gt; are each independently a monovalent organic group having 1 to 20 carbon atoms, and the plurality of X _{2, which} may be present, (1), wherein m is an integer of 1 to 100, or a structure represented by the following general formula (6):

[Chemical Formula 16]

(Wherein R _{1 s} present in plural are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and R ₃ and R ₄ , which are present in plural numbers, A plurality of R _{8 s} are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a trivalent aromatic group, p is an integer of 1 to 100, and q is (3 to 50)}, or a structure represented by the general formula (5) and a structure represented by the general formula (6).

In the general formulas (4) and (6), the diamine-derived site is, for example, 4,4- (diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone, (Diaminodiphenyl) sulfone, and the like. In the general formulas (4) and (5), the acid anhydride-derived moiety is an acid anhydride having a tetravalent organic group X ₁ (X ₁ is as defined above) and a tetravalent organic group X ₂ (X ₂ is as defined above. The diamine-derived site in the structure represented by the general formula (5) is derived from a diamino (poly) siloxane represented by the general formula (9).

From the viewpoints of the heat resistance and the YI value reduction and the total light transmittance, the unit 1 and the unit 2,

A moiety derived from at least one selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic acid dianhydride (BPDA)

4,4'-oxydiphthalic dianhydride (ODPA), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid 2 (CHDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), 4,4'-biphenylbis (trimellitic acid monoester acid anhydride) (TAHQ), and (9), 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF)

Is preferably at least 60 mol%, more preferably at least 65 mol%, and even more preferably at least 70 mol%, based on the total amount of the acid anhydride-derived sites of the unit 1 and the unit 2 Included in quantities.

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

The resin precursor according to the present embodiment may contain, if necessary, a compound represented by the following general formula (7):

[Chemical Formula 17]

(Wherein R _{1 s} present in plural numbers are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and X _{3, which} may be present in plural numbers, And a plurality of X _{4 which} may be present are each independently a tetravalent organic group having 4 to 32 carbon atoms and t is an integer of 1 to 100. The unit 3 having the structure represented by May be further contained.

Unit 3 is a structure in which the diamine-derived site is a site derived from a diamine other than the compound selected from the group consisting of 4,4-DAS, 3,4-DAS, 3,3-DAS, and silicon-containing diamine.

In the unit 3, R ₁ is preferably a hydrogen atom. X ₃ is preferably a divalent aromatic group or alicyclic group from the viewpoints of heat resistance, reduction of the YI value, and total light transmittance. X ₄ is preferably a divalent aromatic group or an alicyclic group from the viewpoints of heat resistance, reduction of the YI value, and total light transmittance. Among them, it is preferable that X ₃ is a residue which is a structure excluding 2,2'-bis (trifluoromethyl) benzidine from the amino group. The organic groups X ₁ , X ₂ and X ₄ may be the same or different.

The mass ratio of the unit 3 in the resin precursor according to the present embodiment is preferably 80% by mass or less, and more preferably 70% by mass or less, from the viewpoint of reduction in oxygen dependency of YI value and total light transmittance.

The resin precursor according to the present embodiment is obtained by heat-curing the resin precursor at 300 to 500 占 폚 in an inert atmosphere (for example, under an atmosphere of nitrogen or argon) or a resin precursor thereof at 350 占 폚 Wherein the resin obtained by the heat curing has a glass transition temperature of at least one of a glass transition temperature of at least one of the range of -150 ° C to 0 ° C and a glass transition temperature of 150 ° C to 380 ° C and has a glass transition temperature of more than 0 ° C and less than 150 ° C It is preferable that it does not have a glass transition temperature. The presence of the glass transition temperature in the range of -150 ° C to 0 ° C and the range of 150 ° C to 380 ° C is preferable from the viewpoint of improving the balance between the residual stress and the total light transmittance. From the viewpoint of heat resistance, the glass transition temperature in the region of 150 ° C to 380 ° C is more preferably in the range of 200 to 380 ° C, and more preferably in the region of 250 to 380 ° C. The resin precursor having the block 1 and the block 2 described later is advantageous in the formation of such a resin precursor.

The resin precursor according to the present embodiment is preferably composed of block 1 consisting mainly of unit 1 and block 2 consisting mainly of unit 2 from the viewpoint of improving heat resistance. Further, the resin precursor may include the above-described unit 3 in the block 1. These blocks may be alternately bonded in the polymer chain or may be bonded in a permutation.

The above-described block 1 contributes to the expression of Tg in the range of 150 to 380 DEG C in the polyimide obtained by thermally curing the resin precursor of the present embodiment. Therefore, it is preferable that the block 1 is a block composed of only the repetition of the unit 1 described above, but it does not exclude that the unit 3 includes the unit 3 other than the unit 1 in the range capable of expressing the target Tg.

Similarly, the above-mentioned block 2 contributes to the expression of Tg in the range of -150 to 0 캜 in the polyimide obtained by heat-curing the resin precursor of the present embodiment. Therefore, it is preferable that the block 2 is a block consisting of only the repetition of the above-described unit 2, but it does not exclude that it includes a unit other than the unit 2 in the range capable of expressing the target Tg.

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

The ratio defined by a value obtained by dividing the sum of the number of repetitions of unit 1 and unit 3 in block 1 by the number of repetitions of unit 2 in block 2 (hereinafter also referred to as a unit ratio) But it is preferably from 0.5 to 100, more preferably from 10 to 50, As described above, the polyimide which is the cured product of the resin precursor having the block 1 and the block 2 has the glass transition temperature derived from the block 1 in the region A of 150 to 380 占 폚 and the glass transition temperature derived from the block 2 as the? It is in the region B of 150 DEG C to 0 DEG C and the region C between the region A and the region B has an advantage of not having the glass transition temperature. When the value of the above unit ratio is 0.5 or more, the heat resistance of the polyimide resin after curing becomes sufficient, which is preferable. When it is 100 or less, the residual stress can be lowered, which is preferable.

On the other hand, when a high molecular weight silicone compound (specifically, a silicone compound having an average molecular weight of 3,000 or more) is used as the silicon group-containing compound in the polymerization component, even if the above block copolymer is not formed, It is possible to exhibit a low residual stress with the inorganic film while maintaining the glass transition temperature. According to the silicone compound having a high molecular weight, the silicone unit itself has a long-chain siloxane structure, which is considered to have the same effect as the above-mentioned block structure. When the silicone compound has a high molecular weight, the functional group concentration is lowered, so that the molar amount of the silicone compound can exhibit at least the high glass transition temperature and low residual stress.

For example, when the high molecular weight silicone compound is a diamine, the resin precursor may be a copolymer of a unit 1 of the general formula (4) derived from (diaminodiphenyl) sulfone and a unit 2 of the unit 2 of the general formula In addition to incorporation, a polyimide precursor mixture, i.e., a blend of water, is produced in which there is a single polyimide precursor of unit 1 (i.e., the unit 2 is not copolymerized).

Accordingly, the present disclosure also includes a precursor mixture comprising the resin precursor of the present embodiment described above and a further resin precursor (e.g., the unit 1 alone polyimide precursor). Specific examples of the polyimide precursor of the unit 1 alone include the following general formula (8):

[Chemical Formula 18]

(Wherein X _{3, which} may be plural, may be independently a quaternary organic group having 4 to 32 carbon atoms, and plural R _{1 s} may independently be a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms Group, or a monovalent aromatic group, and r is an integer of 1 to 100).

On the other hand, examples of the case where the high molecular weight silicone compound is other than diamine include, for example, in the general formula (3), L ₁ , L ₂ and L ₃ each independently represent an acid anhydride group, , An acid halide group, a hydroxyl group, an epoxy group, or a mercapto group.

In the resin precursor according to the present embodiment, when the polymerization component contains a high molecular weight silicone compound, the polyimide which is a cured product of the resin precursor maintains the glass transition temperature in the range of 150 ° C to 380 ° C at a high level, It is possible to achieve a specific characteristic that the residual stress between the film and the inorganic film can be remarkably reduced.

The number average molecular weight of the resin precursor according to the present embodiment is preferably 3000 to 1000000, more preferably 5000 to 500000, still more preferably 7000 to 300000, and particularly preferably 10000 to 250000. From the viewpoint of satisfactory heat resistance and strength (for example, strong elongation), it is preferable that the molecular weight is 3,000 or more. When the molecular weight is 1,000,000 or less, the solubility in a solvent is satisfactory, It is preferable from the viewpoint that it is possible to apply without application. From the viewpoint of obtaining a 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 in terms of standard polystyrene using gel permeation chromatography.

In a preferred embodiment, the resin precursor may be partially imidized.

The resin precursor of the present embodiment has heat resistance capable of enduring a display manufacturing process including a TFT element device on a colorless transparent polyimide substrate and has a glass transition temperature on the high temperature side of 150 占 폚 to 380 占 폚, A polyimide resin having a residual stress of 10 mu m and a thickness of 25 MPa or less can be formed. In a more preferable embodiment, the resin precursor can form a polyimide resin having a residual stress between the inorganic precursor and the inorganic film at a glass transition temperature of 240 캜 to 380 캜, with a film thickness of 10 탆 and 20 MPa or less. In the polyimide resin, when the glass transition temperature is in the range of -150 to 0 占 폚, this temperature is lower than the room temperature, so that the heat resistance required in an actual display manufacturing process is not affected.

In a preferred embodiment, the resin precursor has the following characteristics.

A solution obtained by dissolving a resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) is developed on the surface of a support and the solution is heated at 300 to 500 ° C ) (For example, 1 hour), the yellow degree of the resin obtained when the resin precursor is imidized is 7 or less at a film thickness of 20 mu m.

A solution obtained by dissolving a resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) is developed on the surface of a support and the solution is heated at 300 to 500 ° C ) (For example, 1 hour), the resin residual stress is 25 MPa or less at a film thickness of 10 mu m in a resin obtained by imidizing the resin precursor.

&Lt; Production of resin precursor &gt;

Next, a method of synthesizing the resin precursor according to the present embodiment will be described. For example, when the resin precursor according to the present embodiment is composed of two blocks as in the above-described block 1 and block 2, the polyimide precursor corresponding to each block is separately prepared, To give a condensation reaction, whereby a resin precursor according to the present embodiment can be obtained. In the case where the end groups of the polyimide precursor in the block of the uniaxial chain are used as the carboxylic acid so that both blocks can be provided in the condensation reaction, the end groups of the polyimide precursor in the other block may be amino groups, , For example, the molar ratio of the tetracarboxylic acid dianhydride and the diamine is controlled. In this method, a polyimide precursor having a more preferable complete block property can be synthesized.

On the other hand, when a tetracarboxylic acid dianhydride as a polymerization raw material is common between block 1 and block 2, an aromatic diamine is used as a raw material for block 1, and a silicon-containing diamine having high reactivity is used as a raw material for block 2, A synthesis method using the reactivity difference of both diamines may become possible. For example, it is possible to prepare a polyimide precursor having a certain degree of blocking property by adding an aromatic diamine and a silicon-containing diamine simultaneously to a previously prepared tetracarboxylic acid dianhydride and providing it to a condensation reaction. In this method, it is not possible to synthesize a block polyimide precursor having a complete block property, but a polyimide precursor having a block property can be synthesized. The reason for having the block property here is that the glass transition temperature corresponding to each block is observed in the polyimide resin after the heat curing, for example, when the polyimide resin is in the range of 4, (Diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone and 3,3- (diaminodiphenyl) sulfone, and the tetracarboxylic acid anhydride Quot; refers to the glass transition temperature of the block 1 derived from the co-polymer, and the glass transition temperature of the block 2 derived from the polycondensation product of the silicon-containing diamine and the tetracarboxylic anhydride.

As described above, in the resin precursor according to the present embodiment, the polyimide resin obtained by thermally curing the resin precursor has blockiness to such an extent that the glass transition temperature can be confirmed in the region A on the high-temperature side and the region B on the low- However, this advantage can be obtained even if the polyimide resin does not have complete blocking property. The above-mentioned advantage of the resin precursor having the blocks 1 and 2 can be obtained even if the glass transition temperature is not confirmed in the region C between the region A and the region B and the unit other than the block 1 and the block 2 is contained It is possible.

Further, by adding N, N-dimethylformamide dimethylacetal or N, N-dimethylformamide diethyl acetal to the polyamic acid as described above and heating the mixture, some or all of the carboxylic acid is esterified, The viscosity stability of the solution containing the resin precursor and the solvent during storage at room temperature may be improved. These ester-modified polyamic acid may be obtained by reacting the above-mentioned tetracarboxylic acid anhydride with one equivalent of an alcohol equivalent to the acid anhydride group in advance, and then adding a dehydrating condensation agent such as thionyl chloride or dicyclohexylcarbodiimide , Followed by condensation reaction with diamine.

<Resin composition>

Another aspect of the present invention provides a resin composition containing a resin precursor or a precursor mixture as described above and a solvent. The resin composition is typically a varnish.

In a more preferred embodiment, the resin composition is prepared by dissolving a carboxylic acid component and a diamine component in a solvent, for example, an organic solvent and reacting the same, and producing a polyamic acid solution containing a polyamic acid and a solvent as an embodiment of the resin precursor can do. The conditions for 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 proceed the reaction of the silicon group-containing compound, heating at 120 DEG C for about 30 minutes is preferable. At the time of the reaction, it is preferable to be an inert atmosphere such as argon or nitrogen.

The solvent is not particularly limited so long as it is a solvent that dissolves the polyamic acid. As the known reaction solvent, there can be used dimethyl carbonate (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide DMSO), acetone, diethyl acetate, Echamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and ECHAMED B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.). Of these, NMP, DMAc, EQUAMIDE M100 and EQUAMIDE B100 are preferable. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform, or a low-absorption solvent such as? -Butyrolactone may be used.

In the resin composition of the present invention, when the obtained polyimide forms an element such as a TFT, 0.01 to 2% by mass of the alkoxysilane compound is contained relative to 100% by mass of the resin precursor in order to give sufficient adhesion with the support Is preferable.

It is preferable that the content of the alkoxysilane compound is 0.01 mass% or more based on 100 mass% of the resin precursor, whereby good adhesion with the support can be obtained and the content of the alkoxysilane compound is 2 mass% . The content of the alkoxysilane compound is more preferably 0.02 to 2% by mass, more preferably 0.05 to 1% by mass, further preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.5% by mass, Is particularly preferable.

Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane ,? -aminopropyltriethoxysilane,? -aminopropyltrimethoxysilane,? -aminopropyltripropoxysilane,? -aminopropyltributoxysilane,? -aminoethyltriethoxysilane,? -aminoethyl Aminoethyltripropoxysilane,? -Aminobutyltriethoxysilane,? -Aminobutyltrimethoxysilane,? -Aminobutyltripropoxysilane,? -Aminobutyltrimethoxysilane,? -Aminobutyltrimethoxysilane, gamma -aminobutyltributoxysilane, and the like, and these may be used in combination of two or more.

After the varnish described above is prepared, the solution may be heated at 130 to 200 ° C for 5 minutes to 2 hours to partially dehydrate the polymer so that the polymer does not precipitate. By controlling temperature and time, the imidization rate can be controlled. By performing partial imidization, the viscosity stability of the resin precursor solution at room temperature can be improved. From the viewpoint of the solubility of the resin precursor in the solution and the storage stability of the solution, the imidization rate is preferably in the range of 5% to 70%.

In a preferred embodiment, the resin composition has the following characteristics.

A resin obtained by imidizing a resin precursor contained in a resin composition by heating the resin composition on the surface of a support and then heating the resin composition at 300 ° C to 500 ° C under a nitrogen atmosphere (or by heating at 350 ° C under a nitrogen atmosphere) The yellowing degree at a film thickness of 20 mu m is 7 or less.

A resin obtained by imidizing a resin precursor contained in a resin composition by heating the resin composition on the surface of a support and then heating the resin composition at 300 ° C to 500 ° C under a nitrogen atmosphere (or by heating at 350 ° C under a nitrogen atmosphere) The residual stress at a film thickness of 10 mu m is 25 MPa or less.

&Lt; Resin film &

Another embodiment of the present invention provides a cured product of the above-mentioned resin precursor or a cured product of the above-mentioned precursor mixture, or a resin film which is a cured product of the above-mentioned resin composition.

In another aspect of the present invention, there is provided a method for producing a resin composition, comprising the steps of:

Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film,

A step of peeling the resin film from the support

And a method for producing the resin film.

In a preferred embodiment of the method for producing a resin film, a polyamic acid solution obtained by dissolving an acid anhydride component and a diamine component in an organic solvent and reacting can be used as the resin composition.

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

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

Here, the developing method includes, for example, a known application method of a spin coat, a slit coat, and a blade coat. After the polyamic acid solution is spread on the adhesive layer, the heat treatment is conducted for a period of 1 minute to 300 minutes at a temperature of 300 ° C or lower for the purpose of mainly removing the solvent, And then heat-treated at a temperature of 550 DEG C for 1 minute to 300 minutes to polyimide the resin precursor. In the case of producing a conventional achromatic transparent polyimide film, it is necessary to control the oxygen concentration in the oven to 100 ppm or less from the viewpoints of reduction in YI value and total light transmittance. According to the resin precursor in the present embodiment , Management of 500 ppm or less is sufficient. From the viewpoint of reducing the YI value and improving the total light transmittance, the oxygen concentration is preferably 1000 ppm or less.

The thickness of the resin film according to the present embodiment is not particularly limited, and is preferably in the range of 10 to 200 占 퐉, and more preferably in the range of 10 to 50 占 퐉.

It is preferable that the resin film according to the present embodiment has a yellowness degree of 7 or less at a film thickness of 20 mu m. It is also preferable that the residual stress is 25 MPa or less at a film thickness of 10 mu m. Particularly, it is more preferable that the degree of yellowness at a film thickness of 20 mu m is 7 or less and the residual stress at a film thickness of 10 mu m is 25 MPa or less. Such characteristics can be satisfactorily realized, for example, by imidizing the resin precursor of the present disclosure under a nitrogen atmosphere at 300 ° C to 500 ° C, more particularly at 350 ° C.

<Laminate>

Another aspect of the present invention provides a laminate comprising a support and a resin film which is formed on the surface of the support and is a cured product of the resin composition described above.

In another aspect of the present invention, there is provided a method for producing a resin composition, comprising the steps of:

Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film and thereby obtaining a laminate including the support and the resin film

The present invention also provides a method for producing a laminate.

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

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

Accordingly, another aspect of the present invention provides a flexible device material comprising the resin precursor described above, or a mixture of the precursors described above.

As described above, since the resin precursor according to the present embodiment has a specific structure, it is possible to form a resin film which is opaque, without requiring any special combination of solvents. Also, the yellowness (YI value) and the total light transmittance of the obtained resin film are less dependent on the oxygen concentration at the time of curing. In addition, it has a low residual stress generated between the resin film and the inorganic film, has a practical glass transition temperature capable of enduring 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 use in a transparent substrate of a flexible display.

More specifically, in the case of forming a flexible display, a flexible substrate is formed thereon using a glass substrate as a support, and a TFT or the like is formed thereon. The step of forming the TFT on the substrate is typically carried out at a temperature in a wide range of 150 to 650 DEG C, but in order to achieve a desired performance in practice, an inorganic material is used mainly in the vicinity of 250 DEG C to 350 DEG C, -IZZO (InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si-TFT).

At this time, if the residual stress generated in the flexible substrate and the polyimide film is high, when the glass substrate is expanded in the high temperature TFT process and then shrunk upon cooling at room temperature, the glass substrate may be warped or broken, . Generally, since the coefficient of thermal expansion of the glass substrate is smaller than that of the resin, residual stress is generated between the glass substrate and the flexible substrate. In consideration of this point, the resin film according to the present embodiment preferably has a residual stress of 25 MPa or less between the resin film and the glass based on the film thickness of 10 mu m.

When the transmittance of the resin film according to the present embodiment is measured with an ultraviolet spectrophotometer based on the thickness of 20 m of the film and the yellowness of 7 or less and the thickness of the film of 20 m, It is preferable that the transmittance at 550 nm is 85% or more. In addition, it is advantageous to obtain a resin film having a low YI value stably, which is less dependent on the oxygen concentration in the oven used for producing the thermosetting film. The YI value of the thermosetting film at an oxygen concentration of 500 ppm or less Is preferably stable.

The resin film according to the present embodiment is more preferable to have a mechanical elongation of 30% or more based on the thickness of the film of 20 占 퐉, from the viewpoint of improving yield in terms of excellent breaking strength when handling a flexible substrate .

It is preferable that the resin film according to the present embodiment has a glass transition temperature of 250 DEG C or higher in order to prevent softening of the resin substrate at a temperature at which the TFT element is manufactured.

It is preferable that the resin film according to the present embodiment is provided with a chemical resistance that can withstand the photoresist stripping solution in the photolithography process used for manufacturing the TFT device.

There are two types of light extraction systems of the flexible display: a top emission system for extracting light from the surface side of the TFT element; and a bottom emission system for extracting light from the back side. In the top-emission method, since the TFT element is not disturbed, the aperture ratio can be easily increased, and the bottom emission system is characterized in that it is easy to align and easy to manufacture. If the TFT element is transparent, the aperture ratio can be improved even in the bottom emission system. Therefore, it is expected that a bottom emission system which is easy to manufacture is adopted in the large organic EL flexible display. When a resin substrate is used for a colorless transparent resin substrate used in the bottom emission system, since a resin substrate comes to the viewer side, optical retardation (Rth) in the thickness direction derived from optical isotropy, It is required in terms of improvement. In the case of using in the top-emission method, it is not required that Rth is low, but it is considered that a material having a low Rth is preferable from the viewpoint that it can be commonly used in both methods. Specifically, the thickness is preferably 200 nm or less, more preferably 90 nm or less, more preferably 80 nm or less, and particularly preferably 50 nm or less to be. When Rth is not more than 100 nm and not more than 90 nm, it satisfies the performance for application to not only the transparent substrate for the top-emission type flexible display but also the transparent substrate for the bottom-emission type flexible display or the electrode substrate for the touch panel .

Another aspect of the present invention provides a polyimide resin film for use in the manufacture of a display substrate, wherein the polyimide resin film has a Rth of 20 to 90 nm at a thickness of 20 占 퐉.

Another aspect of the present invention is a method for producing a polyimide precursor, comprising the steps of: developing a resin composition comprising a polyimide precursor on a surface of a support;

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

A step of forming an element on the polyimide resin film,

A step of peeling the polyimide resin film on which the element is formed from the support

The present invention also provides a method of manufacturing a display substrate.

The resin film according to the present embodiment satisfying the above physical properties is suitably used as a colorless transparent substrate for use in a limited use due to the yellow color of a conventional polyimide film, particularly for a flexible display. (For example, a TFT-LCD interlayer, a gate insulating film, and a liquid crystal alignment film), an ITO substrate for a touch panel, a cover glass replacement resin for a smartphone, Colorless transparency of a substrate or the like can also be used in fields requiring low birefringence. When a polyimide according to the present embodiment is applied as a liquid crystal alignment film, a TFT-LCD having a high contrast ratio can be produced, contributing to an increase in the aperture ratio.

The resin film and the laminate produced using the resin precursor according to the present embodiment can be suitably used as a substrate, for example, in the production of a semiconductor insulating film, a TFT-LCD insulating film, an electrode protecting film, and a flexible device . Here, the flexible device includes, for example, a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, a flexible light, and a flexible battery.

Example

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

Various evaluations in Examples and Comparative Examples were carried out as follows.

(Measurement of weight average molecular weight)

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions. As a solvent, 24.8 mmol / l lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.5%) was added to the solution, using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, ) And 63.2 mmol / l phosphoric acid (for high-speed liquid chromatograph, manufactured by Wako Pure Chemical Industries, Ltd.) were added. The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

Column: Shodex KD-806M (manufactured by Showa Denko KK)

Flow rate: 1.0 ml / min

Column temperature: 40 DEG C

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)

        UV-2075Plus (UV-VIS: ultraviolet visible light absorber, manufactured by JASCO)

(Silicon group-containing monomer concentration)

The concentration of the silicon group-containing monomer was calculated from the following formula using the mass of each of the silicon-containing monomer, polyvalent carboxylic acid or derivative thereof, and diamine compound used in synthesizing the resin precursor.

Silicon group-containing monomer concentration (%) = Silicon group-containing monomer mass / (Silicon group-containing monomer mass + Polybasic carboxylic acid or its derivative + Mass of diamine compound) × 100

(Production of laminate and insulating film)

The resin composition was applied to a non-alkali glass substrate (0.7 mm thick) with a bar coater and leveling was carried out at room temperature for 5 minutes to 10 minutes. A vertical curing oven (model name VF-2000B manufactured by Koyo Lindberg) Heated at 140 占 폚 for 60 minutes and further heated at 350 占 폚 for 60 minutes in a nitrogen atmosphere to prepare 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 dependence of the YI value and the total light transmittance on the oxygen concentration was examined. The film thickness of the resin composition of the laminate was 20 mu m. After curing at 350 DEG C (curing treatment), the laminate was allowed to stand at room temperature for 24 hours, the resin film was peeled from the glass, and the film was isolated. The degree of yellowness below that of the total light transmittance was evaluated by adjusting the oxygen concentration in the hot air oven to 100 ppm and curing the resin film at 350 DEG C for 60 minutes as a sample.

(Evaluation of tensile elongation)

A resin film having a sample length of 5 占 0 mm and a thickness of 20 占 퐉 cured at 350 占 폚 was stretched at a speed of 100 mm / min using a tensile tester (RTG-1210, manufactured by A & Respectively.

(Yellowness, total light transmittance and its dependency on curing oxygen concentration)

A resin film having a thickness of 20 占 퐉 and cured at 350 占 폚 was adjusted to 50 ppm, 100 ppm and 500 ppm respectively in the oven using a D65 light source with Spectrophotometer SE600 manufactured by Nippon Denko Kogyo Co., , And the yellowness index (YI value) and the total light transmittance were measured.

(Evaluation of thickness direction retardation (Rth)

A resin film having a thickness of 20 占 퐉 and cured at 350 占 폚 was measured using a phase difference birefringence measurement apparatus (KOBRA-WR manufactured by Oji Paper Measuring Instruments Co., Ltd.). The wavelength of the measurement light was 589 nm.

(Evaluation of glass transition temperature, linear expansion coefficient)

With respect to the measurement of the glass transition temperature (referred to as Tg (1)) and the coefficient of linear expansion (CTE) in the room temperature region or more, a resin film having a sample length of 5 × 50 mm and a thickness of 20 μm, (Flow rate: 20 ml / min.) At a temperature of 50 to 450 占 폚 under a load of 5 g, a temperature raising rate of 10 占 폚 / min and a nitrogen atmosphere by thermomechanical analysis using a thermomechanical analyzer (TMA- And the CTE of the heat-resistant resin film at 100 to 250 占 폚 was obtained by calculating the inflection point as the glass transition temperature.

Since the above method can not measure the glass transition temperature (referred to as Tg (2)) in the room temperature region or below, the resin film is measured at a temperature in the range of -150 캜 to 400 캜 using a dynamic viscoelasticity measuring apparatus Infra-red in the temperature range below room temperature of E-prime was measured by means of RHEOVIBRON MODEL RHEO-1021 manufactured by Mitsubishi Chemical Corporation, and the inflection point thereof was determined as the glass transition temperature at low temperature.

(Evaluation of Residual Stress)

The resin composition was coated on a 6-inch silicon wafer having a thickness of 625 占 퐉 占 25 占 퐉 and a thickness of 625 占 퐉 占 25 占 퐉, which had been previously measured for "bending amount", using a residual stress measuring apparatus (manufactured by Tencor Corporation, model name FLX-2320) , Pre-baked at 140 占 폚 for 60 minutes, and subjected to a heat curing treatment at 350 占 폚 for one hour in a nitrogen atmosphere using a vertical cure (manufactured by Koyo Lindberg Co., model name VF-2000B) A silicon wafer with a resin film having a thickness of 10 mu m was produced. The warpage of the wafer was measured using the residual stress measuring apparatus described above, and the residual stress generated between the silicon wafer and the resin film was evaluated.

(Evaluation of chemical resistance test)

A resin film piece having a thickness of 20 占 퐉 and cured at 350 占 폚 was immersed in an NMP layer at room temperature and lifted every 10 minutes and washed with ion-exchanged water. The surface of the film was observed with a microscope, The formation time was evaluated at intervals of 10 minutes up to 300 minutes.

[Example 1]

1000 g of NMP was added while introducing nitrogen gas into a 3 L separable flask equipped with a stirring bar equipped with an oil bath to obtain 232.4 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) Followed by addition of 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic acid anhydride 1), followed by stirring at room temperature for 30 minutes. After the temperature was raised to 50 占 폚 and the mixture was stirred for 12 hours, 105.6 g of both terminal amine-modified methylphenyl silicone oil (X22-1660B-3 (number average molecular weight: 4400) 298 g, and added dropwise using a dropping funnel. After raising the temperature to 80 DEG C and stirring for 1 hour, the oil bath was removed and returned to room temperature to obtain an NMP solution of a transparent polyamic acid (hereinafter also referred to as a varnish). The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1. Table 4 shows the test results of the cured film at 350 占 폚.

[Examples 2 to 33, 49 to 58]

In the same manner as in Example 1, the same operations as in Example 1 were carried out except that the diamine 1, the tetracarboxylic acid anhydride 1, the kind of the diamine containing silicon group, and the mass added thereof were changed to those shown in Table 1, . The amounts of NMP shown in Tables 1 and 2 indicate the total amount of NMP finally contained in the varnish and the mass including 298 g of NMP to dilute the silicon group-containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Tables 1, 2 and 7, respectively. The test results of the cured film at 350 占 폚 are shown in Tables 4, 5 and 8, respectively. The names of the official compounds of the abbreviated compounds listed 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 acid dianhydride

ODPA: 4,4'-oxydiphthalic acid dianhydride

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

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride

CHDA: Cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride

DSDA: 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride

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

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

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

BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride

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

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

FM3311: Amine-modified dimethyl silicone oil at both ends (Sir Plane FM3311 (number average molecular weight 1000) manufactured by Chisso Corporation)

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

TACl: Anhydrous trimellitic acid chloride

[Example 34]

Nitrogen gas was introduced into a 3 L separable flask equipped with a stirrer bar equipped with an oil bath, 1274 g of NMP was added, and 4,4'-oxydiphthalic dianhydride (hereinafter referred to as ODPA) (tetracarboxylic acid And 105.6 g of a double-ended amine-modified methylphenyl silicone oil (X22-1660B-3 manufactured by Shin-Etsu Chemical Co., Ltd. (number average molecular weight: 4400)) (defined as a diamine containing silicon group) Dissolved in 298 g of NMP was added dropwise using a dripping funnel. After stirring for 1 hour at room temperature, 149.9 g of 2,2'-bis (trifluoromethyl) benzidine (hereinafter referred to as TFMB) (defined as diamine 2) was added with stirring, and then 3,3- DAS was added with stirring to 116.2 g, and the mixture was stirred at room temperature for 1 hour. Subsequently, the mixture was heated to 50 DEG C, 147.1 g of BPDA (defined as tetracarboxylic acid anhydride 2) was added, and the mixture was stirred for 12 hours. The mixture was heated to 80 DEG C and stirred for 4 hours, and then the oil bath was removed and returned to room temperature to obtain a transparent polyamic acid NMP solution (hereinafter also referred to as a varnish). The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2. Table 5 shows the test results of the cured film at 350 占 폚.

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

In the same manner as in Example 34, the kind of diamine 1, diamine 2, tetracarboxylic acid anhydride 1, tetracarboxylic acid anhydride 2, and their added mass were changed to those shown in Table 2, To obtain a varnish. The addition amount of NMP shown in Table 2 indicates the total amount of NMP finally contained in the varnish and is a mass including 298 g of NMP to dilute the silicon group-containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. Table 5 shows the test results of the cured film at 350 占 폚.

[Example 36]

1196 g of N-methylpyrrolidone (hereinafter referred to as NMP) was added to a 3 L separable flask equipped with a stirrer bar equipped with an oil bath while introducing nitrogen gas, and 3,3 - (diaminodi Phenyl) sulfone (defined as diamine 1) was added with stirring to 232.4 g, and after heating to 50 DEG C, 147.1 g of BPDA (defined as tetracarboxylic acid anhydride 1) was added and stirred for 30 minutes. Subsequently, 155.1 g of ODPA (defined as tetracarboxylic anhydride 2) was added, and the mixture was stirred for 8 hours. Thereafter, a double-ended amine-modified methylphenyl silicone oil (X22-1660B-3 manufactured by Shin-Etsu Chemical Co., Containing diamine) was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After raising the temperature to 80 DEG C and stirring for 1 hour, the oil bath was removed and returned to room temperature to obtain an NMP solution of a transparent polyamic acid (hereinafter also referred to as a varnish). The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2. Table 5 shows the test results of the cured film at 350 占 폚.

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

The same operations as in Example 36 were carried out in the same manner as in Example 36 except that the diamine 1, the tetracarboxylic acid anhydride 1, the tetracarboxylic acid anhydride 2, and the added mass were changed to those shown in Table 2, respectively I got a varnish. The addition amount of NMP shown in Table 2 indicates the total amount of NMP finally contained in the varnish and is a mass including 298 g of NMP to dilute the silicon group-containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. Table 5 shows the test results of the cured film at 350 占 폚.

[Example 38]

1200 g of NMP was added while introducing nitrogen gas into a 3 L separable flask equipped with a stirring bar equipped with an oil bath to obtain 232.4 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) After heating to 50 캜, 40.6 g of terephthalic acid chloride (hereinafter referred to as other monomer component) was dissolved in 200 g of? -Butyrolactone, followed by dropwise addition, followed by stirring for 30 minutes. Subsequently, 235.4 g of BPDA (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred for 8 hours. Thereafter, both ends amine-modified methylphenyl silicone oil (X22-1660B-3 (number average molecular weight: 4400) Containing diamine) was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After raising the temperature to 80 DEG C and stirring for 1 hour, the oil bath was removed and returned to room temperature to obtain a transparent polyamic acid solution. 1000 g of NMP was added thereto and diluted, and the mixture was added dropwise to 10 liters of ion-exchanged water. Powders of the polyamideimide precursor were precipitated, and the powder was separated by filtration with a Buchner funnel. The powder was vacuum dried at 40 DEG C for 48 hours. 1403 g of NMP was added to the powder thus obtained to obtain an NMP solution of the polyamideimide precursor. The composition and the weight average molecular weight (Mw) of the obtained polyamideimide precursor are shown in Table 2. Table 5 shows the test results of the cured film at 350 占 폚.

[Examples 43, 48]

A varnish was obtained in the same manner as in Example 38 except that the diamine 1, the tetracarboxylic acid anhydride 1, the kinds of the other monomer components, and the addition mass thereof were changed to those shown in Table 2, respectively, . The addition amount of NMP shown in Table 2 represents the total amount of NMP finally included in the varnish. The composition and the weight average molecular weight (Mw) of the obtained polyamideimide precursor are shown in Table 2, respectively. Table 5 shows the test results of the cured film at 350 占 폚.

[Example 59]

To a 3 L separable flask equipped with a stirrer bar equipped with an oil bath, 1000 g of NMP was added while nitrogen gas was introduced, 248.30 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) Followed by addition of 275.13 g of BPDA (defined as tetracarboxylic acid anhydride 1), followed by stirring at room temperature for 30 minutes. The mixture was heated to 50 DEG C and stirred for 12 hours. Thereafter, 104.58 g of a methylphenyl silicone oil modified with both terminal anhydrides (X22-168-P5-B (number average molecular weight: 4200) Was added dropwise using a dropping funnel. After raising the temperature to 80 DEG C and stirring for 1 hour, the oil bath was removed and returned to room temperature to obtain an NMP solution of a transparent polyamic acid (hereinafter also referred to as a varnish). The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 7. Table 8 shows the test results of the cured film at 350 占 폚.

[Examples 60 to 66]

In the same manner as in Example 59, the same operations as in Example 1 were carried out, except that diamine 1, tetracarboxylic acid anhydride 1, types of diamines containing silicon groups, and their addition mass were changed to those shown in Table 1, . The amounts of NMP shown in Tables 1 and 2 indicate the total amount of NMP finally contained in the varnish and the mass including 298 g of NMP to dilute 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. Table 8 shows the test results of the cured film at 350 占 폚.

[Comparative Example 1]

To a 3 L separable flask equipped with a stirrer bar equipped with an oil bath, while introducing nitrogen gas, 1065 g of NMP was added, and 248.3 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) Followed by addition of 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic acid anhydride 1), followed by stirring at room temperature for 30 minutes. The mixture was heated to 50 DEG C and stirred for 12 hours, and then the oil bath was removed and returned to room temperature to obtain a transparent polyamic acid NMP solution (hereinafter also referred to as varnish). The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3. Table 6 shows the test results of the cured film at 350 占 폚.

[Comparative Examples 2 to 21]

In the same manner as in Comparative Example 1, varnishes were obtained in the same manner as in Comparative Example 1, except that the diamine 1, the tetracarboxylic acid anhydride 1, and the added mass were changed to those shown in Table 3, respectively. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3, respectively. Table 6 shows the test results of the cured film at 350 占 폚.

[Comparative Example 22]

Nitrogen gas was introduced into a 3 L separable flask equipped with an oil bath, 1332 g of NMP was added, and 299.8 g of TFMB (defined as diamine 2) was added with stirring, and 294.2 g of BPDA Carboxylic acid anhydride 1) was added, the mixture was heated to 50 占 폚 and stirred for 12 hours. 105.6 g of both terminal amine-modified methylphenyl silicone oil (X22-1660B-3 (number average molecular weight: 4400) (manufactured by Shin-Etsu Chemical Co., Ltd.) (defined as a diamine containing silicon group) was dissolved in 298 g of NMP, . After completion of the dropwise addition, the mixture was heated to 80 DEG C and stirred for 1 hour. Then, the oil bath was removed and returned to room temperature to obtain an opaque polyamic acid NMP solution (hereinafter also referred to as varnish) with slight turbulence. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3. Table 6 shows the test results of the cured film at 350 占 폚.

[Example 23]

4.36 g (0.02 mol) of pyromellitic anhydride (PMDA) and 25.78 g of BTDA were dispersed in 240 g of N-methyl-2-pyrrolidone (NMP) to obtain ω- A solution obtained by dissolving 2.4 g of dimethylsiloxane (average molecular weight 480) in 50 g of diethylene glycol dimethyl ether (Dig) was added dropwise in small portions, and the mixture was reacted for 1 hour with stirring. After diaminosiloxane and tetracarboxylic acid dianhydride were reacted in this manner, 14.62 g (0.05 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R) 11.17 g of DAS was added in small portions as powder.

[Example 24]

A one-liter flask equipped with a stirrer, dropping funnel, thermometer, condenser and nitrogen substitution device was fixed in cold water. 500 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) dehydrated and purified, 3 g of 3,3'4,4'-benzophenonetetracarboxylic acid 2 (0.0773 moles) of 3-aminodiphenylsulfone (BTDA), 15.48 g (0.0623 moles) of 3,3'-diaminodiphenylsulfone (3,3-DAS) and ω- 14.96 g (0.0159 mol) of polydimethylsiloxane (molecular weight 960) were mixed and a polyamic acid solution was obtained according to a conventional method.

[Example 25]

In a 300 ml four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube, 2.87 g (25.1 mmol) of 1,4-diaminocyclohexane as a diamine compound and two terminal amino-modified methylphenyl silicon (X22-1660B- 3) was added 3.42 g (0.8 mmol). Subsequently, the inside of the flask was purged with nitrogen, 58 ml of N, N-dimethylacetamide was added, and the mixture was stirred until it became homogeneous. 8.71 g (25.9 mmol) of diphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride (BPDA) as a polyvalent carboxylic acid derivative was added to the obtained solution at room temperature, and 24 Time agitation was continued to obtain a composition (polyamic acid solution).

[Example 26]

Diamino-2,2'-bis (trifluoromethyl) biphenyl (hereinafter referred to as "bis (trifluoromethyl) biphenyl") as a component (B) was added to a 300 ml four-necked flask equipped with a stirrer, 7.85 g (24.5 mmol) of the amino-modified methylphenyl silicone (X22-9409) and 2.03 g (1.6 mmol) of both terminal amino-modified methylphenylsilicone (X22-9409) were added. Subsequently, the inside of the flask was purged with nitrogen, 58 ml of N, N-dimethylacetamide was added, and the mixture was stirred until it became homogeneous. 5.12 g (26.1 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (hereinafter also referred to as &quot; CBDA &quot;) as a component (A) was added to the obtained solution at room temperature, Followed by stirring at a temperature of 25 deg. C for 24 hours to obtain a composition (polyamic acid solution).

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

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

(1) The residual stress is 25 MPa or less

(2) the yellowness degree is 7 or less, and the influence by the oxygen concentration is small

(3) a glass transition temperature of not lower than 250 占 폚

(4) The total light transmittance is 88% or more, and the influence by the oxygen concentration is small

(5) Tensile elongation 30% or more

(6) NMP chemical resistance test 30 minutes or more

(7) Even when varnish is produced by NMP alone, the thermosetting film is not cloudy, and thus the total light transmittance is high

They satisfy the performance for application to a transparent substrate for a top-emission type flexible display.

Examples 1 to 33, 36, 37, 41, 42, 46, 47, and 53 to 66 are examples in which the retardation Rth in the film thickness direction derived from birefringence is 100 nm or less (20 to 90 nm) Satisfies the performance for application to a transparent substrate for a flexible display of a bottom emission type, a transparent substrate for a flexible display of a bottom emission type, and an electrode substrate for a touch panel. The retardation Rth in the thickness direction was measured by using polyimides (Comparative Examples 1 to 22) in which a silicon-containing monomer was not used as a copolymerizable monomer and polyimides (Examples 1 to 33) using a silicon- It can be seen that the polyimide using the silicon group-containing monomer has a small Rth, and the silicon group-containing monomer contributes to the decrease in 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 were affected by the oxygen concentration at the time of curing and deteriorated.

From these results, it can be seen that the resin obtained from the resin precursor according to the present invention is colorless and transparent, has low residual stress generated with the inorganic film, has excellent chemical resistance, and has a YI value Or a resin film having a small effect on the total light transmittance.

Further, the present invention is not limited to the above-described embodiment, and various modifications can be made.

Industrial availability

INDUSTRIAL APPLICABILITY The present invention can be suitably used as, for example, a substrate for a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, a flexible display, and a substrate for a touch panel ITO electrode.

Claims (39)

As a resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino group reactive group,
Wherein the polymerization component comprises a polyvalent compound having two or more groups selected from an amino group and an amino group reactive group,
Wherein the polyvalent compound comprises a silicon-containing compound,
Wherein the polyvalent compound comprises a diamine represented by the following formula (1)

Wherein the resin precursor is represented by the following general formula (2):

(Wherein, in the formulas, R ₃ and R ₄ , which are plural, are each independently a monovalent organic group having 1 to 20 carbon atoms and h is an integer of 3 to 200)
The content of the silicon group-containing compound is 6% by mass to 25% by mass based on the total mass of the polyvalent compound,
Wherein the resin obtained by heating the resin precursor under an inert atmosphere at a temperature of 300 ° C to 500 ° C has a glass transition temperature of 200 ° C to 380 ° C and has a glass transition temperature in a range of more than 0 ° C and less than 150 ° C Wherein the resin precursor is a resin precursor. The method according to claim 1,
Wherein the amino group-reactive group comprises at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group and an acid anhydride group. The method according to claim 1,
Wherein the silicon-containing compound is represented by the following general formula (3):

Wherein the plurality of R _{2 s} present in plural are independently a single bond or a divalent organic group having 1 to 20 carbon atoms and R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms a plurality to be R ₅ are, to be present, each independently, a monovalent organic group having a carbon number of 1 ~ 20, L _1, L _2, and L ₃ are, each independently, an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, An acid ester group, an acid halide group, a hydroxyl group, an epoxy group, or a mercapto group, j is an integer of 3 to 200, and k is an integer of 0 to 197. The method of claim 3,
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 method of claim 4,
In the general formula (3), L ₁ and L ₂ together are an amino group. The method according to claim 1,
Wherein the resin precursor contains unit 1 and unit 2,
Wherein the unit 1 is represented by at least the following general formula (4);

(Wherein R _{1 s} present in plural numbers are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and X _{1, which} may be present in plural numbers, 32, and n is an integer of 1 to 100,
And the unit 2 is represented by the following general formula (5):

Wherein the plurality of R _{1 s} present are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and the plurality of R _{2 s} present may be independently selected from the group consisting of 3 to 20 carbon atoms And R &lt; ₃ &gt; and R &lt; ₄ &gt; are each independently a monovalent organic group having 1 to 20 carbon atoms, and the plurality of X _{2, which} may be present, (1), wherein m is an integer of 1 to 100, or a structure represented by the following general formula (6):

(Wherein R _{1 s} present in plural are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and R ₃ and R ₄ , which are present in plural numbers, A plurality of R _{8 s} are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a trivalent aromatic group, p is an integer of 1 to 100, and q is Is an integer of 3 to 50, or a resin precursor having both of a structure represented by the general formula (5) and a structure represented by the general formula (6). The method according to claim 6,
Wherein a total amount of the unit 1 and the unit 2 is 30 mass% or more based on the total mass of the resin precursor. The method according to claim 6,
Wherein the resin precursor is represented by the following general formula (7):

(Wherein R _{1 s} present in plural numbers are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and X _{3, which} may be present in plural numbers, And a plurality of X _{4 which} may be present are each independently a tetravalent organic group having 4 to 32 carbon atoms and t is an integer of 1 to 100. The unit 3 having the structure represented by Further comprising a resin precursor. 9. The method of claim 8,
In the above general formula (7), X ₃ is a residue which is a structure excluding an amino group from 2,2'-bis (trifluoromethyl) benzidine. The method according to claim 6,
The unit 1 and the unit 2
A moiety derived from at least one selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic acid dianhydride (BPDA)
4,4'-oxydiphthalic dianhydride (ODPA), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid 2 (CHDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), 4,4'-biphenylbis (trimellitic acid monoester acid anhydride) (TAHQ), and (9), 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF)
Is contained in an amount of 60 mol% or more based on the total amount of the units derived from the acid dianhydrides of the unit 1 and the unit 2. The method according to claim 1,
The resin precursor in which h in the general formula (2) is 10 to 200. The method according to claim 1,
R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group of 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms. The method according to claim 1,
And at least a part of R ₃ and R ₄ is a phenyl group. The method according to claim 1,
A resin precursor comprising a portion derived from biphenyltetracarboxylic acid dianhydride (BPDA) in an amount of 20 mol% or more based on the total amount of the acid anhydride-derived sites of the resin precursor. The method according to claim 1,
A resin precursor partially imidated. A polyimide cured film substrate obtained by curing the resin precursor according to any one of claims 1 to 15. 17. The method of claim 16,
Wherein the polyimide cured film substrate is a polyimide cured film substrate obtained by curing the resin precursor on a support and then peeling from the support. A device comprising the polyimide cured film substrate according to claim 16. 19. The method of claim 18,
Wherein the device is a flexible device. A display comprising the polyimide cured film substrate according to claim 16. 21. The method of claim 20,
Wherein the display is a flexible display. A touch panel electrode substrate comprising the polyimide cured film substrate according to claim 16. 23. The method of claim 22,
Wherein the touch panel electrode substrate is a flexible touch panel electrode substrate. A solar cell comprising the polyimide cured film substrate according to claim 16. 25. The method of claim 24,
Wherein the solar cell is a flexible solar cell. A lighting comprising the polyimide cured film substrate according to claim 16. 27. The method of claim 26,
Wherein the illumination is a flexible illumination. A battery comprising the polyimide cured film substrate according to claim 16. 29. The method of claim 28,
Wherein the battery is a flexible battery. A resin composition comprising the resin precursor according to claim 1 and a compound represented by the following general formula (8):

(Wherein X _{3, which} may be plural, may be independently a quaternary organic group having 4 to 32 carbon atoms, and plural R _{1 s} may independently be a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms , Or a monovalent aromatic group, and r is an integer of 1 to 100. A precursor mixture comprising a resin precursor having a structure represented by formula A flexible device material comprising the resin precursor according to any one of claims 1 to 15 or the precursor mixture according to claim 30. A resin film which is a cured product of the resin precursor according to any one of claims 1 to 15 or a cured product of the precursor mixture according to claim 30. A resin composition comprising the resin precursor according to any one of claims 1 to 15 or the precursor mixture according to claim 30, and a solvent. 34. The method of claim 33,
After the resin composition is developed on the surface of the support, the resin composition is heated at 300 ° C to 500 ° C under a nitrogen atmosphere to imidize the resin precursor contained in the resin composition. And the yellowness degree is 7 or less. 34. The method of claim 33,
The resin composition is developed on the surface of a support, and then the resin composition is heated at 300 ° C to 500 ° C under a nitrogen atmosphere to imidize the resin precursor contained in the resin composition. And a residual stress of 25 MPa or less. A resin film which is a cured product of the resin composition according to claim 33. 32. A method for producing a resin composition, comprising the steps of: developing the resin composition according to claim 33 on a surface of a support;
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film;
A step of peeling the resin film from the support
Wherein the resin film comprises a resin. A laminate comprising a support and a resin film which is a cured product of the resin composition according to claim 33 formed on the surface of the support. 33. A method for producing a resin composition, comprising the steps of: developing a resin composition according to claim 33 on a surface of a 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 thereby obtaining a laminate including the support and the resin film
And a step of forming the laminate.