KR20200006626A - 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.A transparent resin cured product can be provided without requiring a special combination of solvents, and has low residual stress generated between the inorganic film, excellent chemical resistance, and YI due to oxygen concentration during the curing process. Provided is a resin precursor capable of imparting a cured resin having a small influence on the value and 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 contains a silicon group-containing compound And the polyhydric compound has following formula (1):

Including diamine represented by this, The resin precursor is following General formula (2):

The resin precursor which has a structure shown by the above, and whose quantity of the silicon-group containing compound is 6 mass%-25 mass% on the basis of the total mass of the polyvalent compound.

Description

RESIN PRECURSOR, RESIN COMPOSITION CONTAINING SAID RESIN PRECURSOR, RESIN FILM, METHOD FOR PRODUCING SAID RESIN FILM, LAMINATE, AND METHOD FOR PRODUCING SAID LAMINATE}

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

Generally, the polyimide (PI) resin film is used as a resin film for the application | requirement with which high heat resistance is calculated | required. The general polyimide resin is produced by solution polymerization of an aromatic dianhydride and an aromatic diamine, preparing a polyimide precursor, and then ring-dehydrating at high temperature, thermally imidizing, or chemically imidizing using a catalyst. It is a heat resistant resin.

The polyimide resin is an insoluble and insoluble super heat resistant resin, and has excellent properties such as heat oxidizing resistance, heat resistance, radiation resistance, low temperature resistance and chemical resistance. For this reason, polyimide resins are used in a wide range of fields including electronic materials, such as insulating coatings, insulating films, semiconductors, and electrode protective films of TFT-LCDs, and in recent years, glass substrates that have conventionally been used in the field of display materials such as liquid crystal alignment films. Instead, the adoption of a colorless transparent flexible substrate using its lightness and flexibility has also been considered.

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

For the problem of improving the transparency of such polyimide, for example, in Non-Patent Document 1, a polyimide having improved the transmittance and transparency of a color by using an acid dianhydride containing a specific structure and a diamine containing a specific structure Meade is described. In addition, in patent documents 1-4, 4, 4-bis (diamino diphenyl) sulfone (it describes also as 4, 4-DAS hereafter) and 3, 3-bis (diamino diphenyl) sulfone (following, 3) The polyimide which improved the transmittance | permeability and the transparency of color is described by using the acid dianhydride containing also a (3-DAS) and specific structure.

Moreover, the polyimide which expresses high Tg, transparency, high adhesiveness, and low curvature by copolymerizing specific aromatic tetracarboxylic dianhydride, alicyclic diamine, and silicon containing diamine in Examples 9 and 10 of the following patent documents 6 Polyimide precursors capable of producing are described.

In addition, in Example 3 of the following patent document 7 and Example 3 of the patent document 8, the polyimide precursor which copolymerized aromatic tetracarboxylic dianhydride, bis (diaminodiphenyl) sulfone, and silicon-containing diamine is semiconductor. It is described to use as a protective resin and the photosensitive resin composition.

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

 Latest Polyimide (Foundation and Application), Japan Polyimide Study Part, P152

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

For example, when using a polyimide resin for the colorless transparent substrate for flexible displays, in order to form a polyimide film on support glass (henceforth a support body), and to manufacture TFT element normally on this polyimide film, In some cases, an inorganic film may be formed. When the coefficient of linear expansion of the polyimide (hereinafter also referred to as CTE) is high, residual stresses are generated between the polyimide film and the inorganic film due to mismatches of the CTE between the inorganic film or the support glass and the polyimide film. Therefore, there exists a problem that a support glass bends or the performance of a TFT element falls. For this reason, in order to improve the curvature of a support glass, there exists a subject that the residual stress of a polyimide is made low. In the polyimide of patent documents 1-4, when residual stress was high and it applied to the colorless transparent substrate for flexible displays, there existed a subject that support glass bends.

Moreover, in order to manufacture a polyimide film, a polyimide precursor is apply | coated on a glass substrate, for example, the glass substrate in which the polyimide precursor was apply | coated was put into the oven which nitrogen gas was introduce | transduced, and 250 degreeC-400 degreeC It is generally necessary to heat the furnace (hereinafter also referred to as a cure process). In the polyimide which improved the transparency of the transmittance | permeability and color of patent documents 1-4 and nonpatent literature 1, when oxygen concentration in the oven of a cure is high, specifically, when oxygen concentration is 100 ppm or more, YI There existed the subject of oxygen concentration dependence that a value raises or total light transmittance falls.

In addition, when using a polyimide resin for the colorless transparent substrate for flexible displays, a TFT element is manufactured by the photolithography process using a photoresist normally on the polyimide film. Since the polyimide film (henceforth a polyimide substrate) used for the colorless transparent substrate for flexible displays is exposed to chemical agents, such as a photoresist stripping liquid used at the process of peeling the photoresist included in this process, It is necessary to have chemical resistance to these drugs. In the polyimide which consists of 4, 4-DAS, 3, 3-DAS, and acid dianhydride containing a specific structure as described in patent document 1, at the time of a photoresist peeling process, a minute crack in a polyimide substrate There existed a subject from the chemical-resistance point, such as the polyimide board | substrate becoming cloudy by the formation and the phenomenon that a total light transmittance falls.

Patent Literature 5 describes introducing a flexible silicon-containing diamine by block copolymerization for the purpose of reducing residual stress while maintaining the glass transition temperature and the Young's modulus of the polyimide. However, as described in Comparative Example 4 of Patent Document 5, when the silicon-containing diamine is copolymerized into blocks, phase separation of the silicon portion proceeds unless the polyimide precursor is dissolved using a combination of special solvents, and thus the refractive index is respectively. In the different sea island structure, the structure of the island portion becomes larger, so that the film becomes cloudy and the total light transmittance decreases. In addition, when using a special solvent combination with a low boiling point, after leaving a polyimide precursor solution to apply | coating to a board | substrate, and leaving it to stand for several hours at room temperature, haze may arise and a coating film may become cloudy, and it is necessary to manage the standing time. There was. Thus, in order to manufacture a transparent thermosetting film with the polyimide which block-polymerized silicon-containing diamine, the problem that it is necessary to manage the leaving time after apply | coating a precursor solution after dissolving a precursor using the combination of a special solvent is required. there was.

Moreover, in Examples 9 and 10 of patent document 6, the polyimide precursor obtained by copolymerizing aromatic tetracarboxylic dianhydride, alicyclic diamine, and silicone diamine, and the polyimide obtained from it are described. However, as a result of the present inventors confirming, this polyamide had the problem that yellowness was high, the total light transmittance was low, and yellowness and transmittance were easy to be influenced by the oxygen concentration at the time of polyimide hardening (compare this specification) See example 25).

And patent document 7, 8 describes the polyimide precursor obtained by copolymerizing (diaminodiphenyl) sulfone, aromatic tetracarboxylic dianhydride, and silicone diamine, and the polyimide obtained from it. However, as a result of the present inventors confirming, the mass ratio of the silicon group containing monomer with respect to the gross mass of the silicon group containing monomer, polyhydric carbonate derivative, and the diamine compound used when synthesize | combining a polyimide precursor is appropriate for patent document 7 Therefore, since the residual stress of the polyimide obtained is large and it is inadequate in the process of a display, and there is much about patent document 8, there existed a subject that the obtained polyimide was cloudy and unsuitable for use for a transparent display (Comparative example of this specification) 23, 24).

This invention is made | formed in view of the above-mentioned problem, and can provide a transparent resin hardened | cured material without requiring a special solvent combination, and also the residual stress which arises with an inorganic film is low, and chemical-resistance is An object of the present invention is to provide a resin precursor which is excellent in giving a cured resin having a small influence on the YI value and the total light transmittance due to the oxygen concentration during the curing process. An object of this invention is to provide the resin composition containing this resin precursor, the resin film which hardened this resin composition, its manufacturing method, a laminated body, and its manufacturing method.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, as a result, the heat resistant resin precursor of a specific structure can form the transparent resin hardened | cured material, without requiring the combination of a special solvent, and such a resin diameter The cargo was found to be a resin cured product having a low residual stress between the inorganic membrane, excellent chemical resistance, and small effect on the YI value and total light transmittance due to the oxygen concentration during the curing process. Based on this, the present invention has been achieved. That is, this invention is as follows.

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

The polymerization component contains a polyvalent compound having two or more groups selected from amino groups and amino group reactive groups,

The polyvalent compound contains a silicon group-containing compound,

The polyvalent compound has following formula (1):

[Formula 1]

Containing diamine represented by

The resin precursor has the following general formula (2):

[Formula 2]

It has a structure represented by {In formula, two or more R <_3> and R <_4> is a C1-C20 monovalent organic group each independently, and h is an integer of 3-200.}

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

Its resin precursor.

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

[3] The silicon group-containing compound is represented by the following general formula (3):

[Formula 3]

{In formula, _{two or} more R <_2> is respectively independently a single bond or a C1-C20 divalent organic group, R <_3> and R <_4> is respectively independently a C1-C20 monovalent organic group , R _{5, which} may be present in plural numbers, are each independently a monovalent organic group having 1 to 20 carbon atoms, and 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. Or the resin precursor as described in [2].

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

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

The unit 1 is at least the following general formula (4);

[Formula 4]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, X <_{1> which} may exist in multiple numbers each independently represents C4-C20. 32 is a tetravalent organic group, and n is an integer of 1-100.}

Has a structure represented by

The unit 2 has the following general formula (5):

[Formula 5]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, and _{two or} more R <_2> is respectively independently C3-C20 Is a divalent aliphatic hydrocarbon or a divalent aromatic group, R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and a plurality of each of X _{2, which} may be present, are each independently 4 to 4 carbon atoms. 32 is a tetravalent organic group, l is an integer of 3-50, and m is an integer of 1-100.} The structure represented by the following or general formula (6):

[Formula 6]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, and two or more R <_3> and R <_4> respectively independently represents carbon number R <_{8> which} is a 1-20 monovalent organic group, two or more R <_8> is respectively independently a C3-C20 trivalent aliphatic hydrocarbon or a trivalent aromatic group, p is an integer of 1-100, and q is It is an integer of 3-50.} As described in any one of [1]-[5] which has both a structure represented by the general formula (5), and the structure represented by the said 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% by mass or more based on the total mass of the resin precursor.

[8] The resin precursor has the following general formula (7):

[Formula 7]

{In formula, two or more R <_1> is a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group each independently, X <_{3> which} may exist in multiple numbers each independently represents C4-C20. X _{4 which} may be a 32-valent divalent organic group, and which may exist in multiple numbers each independently is a C4-C32 tetravalent organic group, and t is an integer of 1-100.} The unit 3 which has a structure represented by The resin precursor as described in [6] or [7] which further contains.

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

[10] the unit 1 and the unit 2

A site derived from one or more selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA);

4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid 2 Anhydride (CHDA), 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis (trimelitic acid monoester acid anhydride) (TAHQ), and Sites derived from one or more selected from the group consisting of 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF)

The resin precursor in any one of [6]-[9] containing the site | part which is a combination of these in the quantity of 60 mol% or more based on the total amount of the site | part from the acid dianhydride of this unit 1 and this unit 2.

[11] The compound according to any one of [1] to [10], wherein R ₃ and R ₄ are each independently a C 1 to C 3 monovalent aliphatic hydrocarbon group or a C 6 to C 10 monovalent aromatic hydrocarbon group. The resin precursor described in the above.

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

[13] The resin obtained by heating and curing the resin precursor under conditions of 300 to 500 ° C. under an inert atmosphere is at least one of a glass transition temperature and a region of 150 ° C. to 380 ° C. in at least one of the range of −150 ° C. to 0 ° C. The resin precursor in any one of [1]-[12] which has a glass transition temperature and does not have a glass transition temperature in the area | region larger than 0 degreeC and less than 150 degreeC.

[14] The item of any of [1] to [13], wherein the moiety derived from biphenyltetracarboxylic dianhydride (BPDA) is contained 20 mol% or more based on the total amount of the acid dianhydride-derived site of the resin precursor. The resin precursor described.

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

[16] The resin precursor according to any one of [1] to [15], and the following general formula (8):

[Formula 8]

{In formula, X <_{3> which} may exist in multiple numbers is respectively independently a C4-C32 tetravalent organic group, and two or more R <_1> represents a hydrogen atom and a C1-C20 monovalent aliphatic hydrocarbon each independently. Or a monovalent aromatic group, and r is an integer of 1 to 100.} A precursor mixture containing a resin precursor having a structure represented by}.

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

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

[20] A 20 μm film exhibited by resin obtained by imidizing the resin precursor contained in the resin composition by developing the resin composition on the surface of the support and then heating the resin composition at 300 ° C. to 500 ° C. under a nitrogen atmosphere. The resin composition as described in [19] whose yellowness in thickness is 7 or less.

[21] A 10 μm film exhibited by resin obtained by imidating the resin precursor contained in the resin composition by developing the resin composition on the surface of the support and then heating the resin composition at 300 ° C. to 500 ° C. under a nitrogen atmosphere. The resin composition as described in [19] or [20] whose residual stress in 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 step of developing the resin composition according to any one of [19] to [21] on the surface of the support;

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

Process of peeling this resin film from the support body

Method for producing a resin film comprising a.

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

[25] a step of developing the resin composition according to any one of [19] to [21] on the surface of the support;

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

Method for producing a laminate comprising a.

[26] A polyimide resin film having a Rth of 20 to 90 nm in a thickness of 20 µm as a polyimide resin film used for producing a display substrate.

[27] a step of developing a resin composition containing a polyimide precursor on the surface of the support;

Heating the support and the resin composition to imidize the polyimide precursor to form a polyimide resin film as described in [26],

Forming an element on the polyimide resin film;

Process of peeling the polyimide resin film in which the element was formed from the support body

Method of manufacturing a display substrate comprising a.

Advantageous Effects of Invention According to the present invention, a transparent resin cured product can be provided without requiring a combination of special solvents, and the residual stress generated between the inorganic film is low, excellent in chemical resistance, and at the time of the curing process. A resin precursor is provided which can impart a cured resin having a small influence on the YI value and the total light transmittance by the oxygen concentration.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment (it abbreviates as "embodiment" hereafter) of the illustration of this invention is demonstrated in detail. In addition, this invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary. In addition, the repetition number of the structural unit in the formula of this indication is only intended the number which can contain the said structural unit in the whole resin precursor, unless there is a special mention, Therefore, it intends specific binding styles, such as a block structure, Note that this is not the case. In addition, unless otherwise indicated, the characteristic value described in this indication is intended to be a value measured by the method described in the term of [Example], or an equivalent thereof to the method understood by those skilled in the art.

<Resin precursor>

The resin precursor which concerns on embodiment of this invention,

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

The polymerization component contains a polyvalent compound having two or more groups selected from amino groups and amino group reactive groups,

The polyvalent compound contains a silicon group-containing compound,

The polyvalent compound has following formula (1):

[Formula 9]

Containing diamine represented by

The resin precursor has the following general formula (2):

[Formula 10]

It has a structure represented by {In formula, two or more R <_3> and R <_4> is a C1-C20 monovalent organic group each independently, and h is an integer of 3-200.}

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

The resin precursor is provided.

The polymerization component includes an amino group and an amino group reactive group. The polymerization component includes a polyvalent compound having two or more groups selected from amino groups and amino group reactive groups. 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 may include a polyvalent compound including 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 have a group having reactivity with an amino group. As the amino group reactive group, for example, 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, an epoxy group, and a mercap Earthenware is mentioned. As a compound containing an acidic radical, dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, and acid dianhydride, acid esterified product, acid chloride, etc. of these carboxylic acids are mentioned, for example. . Therefore, the resin precursor of this 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 polyvalent compound contains at least the diamine represented by 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) and 3,4- (diaminodiphenyl) sulfone ( Hereinafter, it may be one or more selected from the group consisting of 3,4-DAS) and 3,3- (diaminodiphenyl) sulfone (hereinafter also referred to as 3,3-DAS).

At least 1 of a polyhydric compound is a silicon group containing compound. The structure represented by General formula (2) is derived from a silicon group containing compound. The quantity of a silicon group containing compound is 6 mass%-25 mass% (henceforth this mass fraction is also called a silicon group containing monomer concentration) on the mass basis of a polyvalent compound. The silicon group-containing monomer concentration is advantageously 6 mass% or more from the viewpoint of sufficiently obtaining the effect of lowering the stress between the resin film and the inorganic film and the lowering effect of the yellowness, and preferably 7 mass% or more, preferably 8 mass% or more. It is more preferable, and it is still more preferable that it is 10 mass% or more. On the other hand, the silicon group-containing monomer concentration is advantageously 25 mass% or less from the viewpoint of improving transparency, lowering the yellowness and obtaining good heat resistance, without causing the resulting polyimide to be cloudy, and preferably 22 mass% or less. It is more preferable that it is 20 mass% or less. From the viewpoint of improving the chemical resistance, YI value, total light transmittance, birefringence, residual stress, and oxygen dependence of optical properties, it is particularly preferable that the silicon group-containing monomer concentration is 10 mass% or more and 20 mass% or less.

In General formula (2), two or more R <_3> and R <_4> is a C1-C20 monovalent organic group each independently. As a C1-C20 monovalent organic group, a C1-C20 monovalent hydrocarbon group, a C1-C20 amino group, a C1-C20 alkoxy group, an epoxy group, etc. are mentioned.

As this C1-C20 monovalent hydrocarbon group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, etc. are mentioned. As this C1-C20 alkyl group, a C1-C10 alkyl group is preferable from a viewpoint of heat resistance and residual stress, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, t -Butyl group, pentyl group, hexyl group, etc. are mentioned. As said C3-C20 cycloalkyl group, a C3-C10 cycloalkyl group is preferable from the said viewpoint, and a cyclopentyl group, a cyclohexyl group, etc. are mentioned specifically ,. As said C6-C20 aryl group, a C6-C12 aryl group is preferable from the said viewpoint, and a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned specifically ,.

As this C1-C20 amino group, an amino group, the substituted amino group (for example, bis (trialkyl silyl) amino group), etc. are mentioned.

As this C1-C20 monovalent alkoxy group, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, etc. are mentioned.

In general formula (2), the polyimide membrane obtained by which two or more R <_3> and R <_4> is a C1-C3 monovalent aliphatic hydrocarbon group or a C6-C10 monovalent aromatic hydrocarbon group each independently is a It is preferable from the viewpoint of having high heat resistance and low residual stress. From this viewpoint, the C1-C3 monovalent aliphatic hydrocarbon is preferably a methyl group, and the C6-C10 aromatic group is preferably a phenyl group.

H in General formula (2) is an integer of 3-200, Preferably it is an integer of 10-200, More preferably, it is an integer of 20-150, More preferably, it is an integer of 30-100, Especially preferably, it is 35- It is an integer of 80. When h is 2 or less, the residual stress of the polyimide obtained from the resin precursor of the present disclosure may deteriorate (that is, increase), and when h exceeds 200, when a varnish containing a resin precursor and a solvent is prepared, Problems may arise such that the varnish is cloudy, or the mechanical strength of the polyimide is lowered.

In the resin precursor of this embodiment, a silicon group containing compound is the following general formula (3):

[Formula 11]

{In formula, _{two or} more R <_2> is respectively independently a single bond or a C1-C20 divalent organic group, R <_3> and R <_4> is respectively independently a C1-C20 monovalent organic group , R _{5, which} may be present in plural numbers, are each independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ , and L ₃ are each independently an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, It is an acid ester group, an acid halide group, a hydroxyl group, an epoxy group, or a mercapto group, j is an integer of 3-200, k is an integer of 0-197. It is preferable to contain the silicone compound shown by the following. In a preferred embodiment, the silicon group-containing compound is a silicone compound represented by the general formula (3).

As a C1-C20 divalent organic group in R <_2> , a methylene group, a C2-C20 alkylene group, a C3-C20 cycloalkylene group, a C6-C20 arylene group, etc. are mentioned. As this C2-C20 alkylene group, a C2-C10 alkylene group is preferable from a viewpoint of heat resistance, residual stress, and cost, and a dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group Etc. can be mentioned. As said C3-C20 cycloalkylene group, a C3-C10 cycloalkylene group is preferable from the said viewpoint, A cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, etc. are mentioned. Especially, a C3-C20 divalent aliphatic hydrocarbon is preferable from the said viewpoint. As this C6-C20 arylene group, a C3-C20 aromatic group is preferable from the said viewpoint, A phenylene group, a naphthylene group, etc. are mentioned.

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). Moreover, R <_5> is synonymous with a C1-C20 monovalent organic group, ie, R <_3> and R <_4>, and a preferable aspect is the same as R <_3> and R <_4> .

In General Formula (3), L ₁ , L ₂ , and L ₃ each independently represent 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 mer It is a capto group.

The amino group may be substituted, and a bis (trialkyl silyl) amino group etc. are mentioned, for example. As a specific example of the compound represented by General formula (3) whose L <_1> , L <_2> and L <_3> are amino groups, Amino terminal-modified methylphenylsilicone (for example, X22-1660B-3 by Shin-Etsu Chemical Co., Ltd. (water Average molecular weight 4,400) and X22-9409 (number average molecular weight 1,300), both terminal amino-modified dimethylsilicone (for example, X22-161A (number average molecular weight 1,600) by the Shin-Etsu Chemical Co., Ltd., X22-161B (number average molecular weight 3,000) ) And KF8012 (number average molecular weight 4,400); BY16-835U (number average molecular weight 900) manufactured by Torre Dow Corning; and cyraplane FM3311 (number average molecular weight 1000) manufactured by Chisso Corp.).

As an example of the compound whose L <_1> , L <_2> and L <_3> is an isocyanate group, the isocyanate modified silicone etc. which are obtained by reacting the said both terminal amino modified silicone and a phosgene compound are mentioned.

As a specific example of the compound whose L <_1> , L <_2> and L <_3> are a carboxyl group, For example, X22-162C (number average molecular weight 4,600) by Shin-Etsu Chemical Co., Ltd., BY16-880 (number average molecular weight 6,600) by Torre Dow Corning Etc. can be mentioned.

As a specific example of the compound whose L <_1> , L <_2> and L <_3> are acid anhydride groups, a following formula group:

[Formula 12]

The acyl compound etc. which have at least 1 of the group shown by these are mentioned.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are an acid anhydride group include X22-168AS (Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-168A (Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000), X22- 168B (Shin-Etsu Chemical make, number average molecular weight 3,200), X22-168-P5-8 (Shin-Etsu Chemical make, number average molecular weight 4,200), DMS-Z21 (Gelest company make, number average molecular weight 600-800), etc. are mentioned. have.

As a specific example of the compound whose L <_1> , L <_2> and L <_3> are acid ester groups, the compound etc. which are obtained by making the said L <_1> , L <_2> and L <_3> react with the compound and alcohol which are a carboxyl group or an acid anhydride group are mentioned.

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

As specific examples of the compound in which L ₁ , L ₂ , and L ₃ are hydroxyl groups, KF-6000 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), KF-6001 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,800), KF- 6002 (Shin-Etsu Chemical make, number average molecular weight 3,200), KF-6003 (Shin-Etsu Chemical make, number average molecular weight 5,000), etc. are mentioned. It is thought that the compound which has a hydroxyl group reacts with the compound which has a carboxyl group or an acid anhydride group.

As a specific example of the compound whose L <_1> , L <_2> and L <_3> are epoxy groups, X22-163 (Shin-Etsu Chemical make, number average molecular weight 400) and KF-105 (Shin-Etsu Chemical make, number average molecular weight) which are both terminal epoxy types 980), X22-163A (Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000), X22-163B (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,500), X22-163C (Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,400); Both terminal alicyclic epoxy X22-169AS (Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-169B (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400); X22-9002 (Shin-Etsu Chemical Co., Ltd., functional group equivalent 5,000) g / mol); It is thought that the compound which has an epoxy group reacts with 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., Ltd., number average molecular weight 3,400), X22-167C (Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,600). Can be mentioned. It is thought that the compound which has a mercapto group reacts with the compound which has a carboxyl group or an acid anhydride group.

It is preferable that L <_1> , L <_2> and L <_3> are an amino group or an acid anhydride group each independently from a viewpoint of the molecular weight improvement of a resin precursor, or the heat resistance of the polyimide obtained, and also contains a resin precursor and a solvent It is more preferable that it is an amino group each independently from a viewpoint of avoiding turbidity of a varnish, or a viewpoint of cost.

Or from a viewpoint of avoiding the turbidity of the varnish containing a resin precursor and a solvent, or a viewpoint of cost, it is preferable that L <_1> and L <_2> are respectively independently an amino group or an acid anhydride group, and k is zero. In this case, it is more preferable that L ₁ and L ₂ are together an amino group.

In General formula (3), the preferable aspect of j is the same as what was mentioned above about h in General formula (2). In General formula (3), k is an integer of 0-197, Preferably it is 0-100, More preferably, it is 0-50, Especially preferably, it is 0-25. When k exceeds 197, when the varnish containing a resin precursor and a solvent is prepared, the problem that the varnish becomes cloudy may arise. When k is 0, it is preferable from a viewpoint of the molecular weight improvement of a resin precursor, or the heat resistance of the polyimide obtained. When k is 0, it is advantageous that j is 3-200 from a viewpoint of the molecular weight improvement of a resin precursor, or the heat resistance of the polyimide obtained.

In a preferred embodiment, in each formula of the present disclosure, R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or 1 to 6 carbon atoms from the viewpoint of residual stress and cost. It is a valent aromatic hydrocarbon group. Or in each formula of this indication, it is preferable that a part of R <_3> and R <_4> is a phenyl group from a viewpoint of heat resistance and a residual stress.

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

<Tetracarboxylic dianhydride>

As tetracarboxylic dianhydride as an example of the polyhydric compound contained in a polymerization raw material, Specifically, C8-36 aromatic tetracarboxylic dianhydride and C6-C36 alicyclic tetracarboxylic acid The compound chosen from the anhydride is preferable from a viewpoint of reduction of a YI value, and total light transmittance.

More specifically, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- (2,5-dioxotetrahydro-3-furanyl) -3- Methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ', 4 , 4'-benzophenonetetracarboxylic dianhydride (hereinafter also referred to as BTDA), 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (hereinafter also referred to as DSDA), 2,2', 3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene- 4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA Thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3- Bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl ) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) Phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter also referred to as BPADA), bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-te Lamethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarb Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarr Acid dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as CBDA Cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter referred to as , CHDA), 3,3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) 2 Anhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2- Ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Dianhydride, 2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicar Dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxyl) Acid) dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel- [1S, 5R, 6R] -3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis- (3,4-dicarboxylic anhydride phenyl) ether, 4,4'- Biphenylbis (trimelitic 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 preferred from the viewpoint of reducing CTE, improving chemical resistance, improving glass transition temperature (Tg), and improving mechanical elongation. Moreover, 6FDA, ODPA, and BPADA are preferable from the viewpoint of lowering yellowness, lowering birefringence and improving mechanical elongation. In addition, BPDA is preferable from the viewpoint of reducing residual stress, lowering of yellowness, lowering of birefringence, improving chemical resistance, improving Tg, and improving mechanical elongation. Moreover, CHDA is preferable from a viewpoint of the reduction of residual stress and the fall of yellowness. Among them, BPDA of rigid structure expressing high chemical resistance, high Tg and low CTE, and tetracarboxylic dianhydride selected from the group consisting of 6FDA, ODPA, and CHDA having low yellowness and birefringence are used in combination. It is preferable from the viewpoint of high chemical resistance, lowering of residual stress, lowering of yellowness, lowering of birefringence, and improvement of total light transmittance.

Especially, in addition to the said effect, from a viewpoint of high elongation, chemical-resistance improvement, and a high Young's modulus, it is preferable that the site | part derived from BPDA is 20 mol% or more of the site | part derived from all the acid dianhydrides, and it is 50 mol% or more. More preferably, it is more preferable that it is 80 mol% or more, and 100% may be sufficient.

<Dicarboxylic acid>

Moreover, in addition to the tetracarboxylic dianhydride mentioned above, the resin precursor in this embodiment is a thing like improvement of mechanical elongation, improvement of glass transition temperature, reduction of yellowness, in addition to the tetracarboxylic dianhydride mentioned above. For the purpose of adjusting performance, the thermosetting film can also be made polyamideimide by introducing a polyamide component by copolymerizing dicarboxylic acid. As such dicarboxylic acid, the dicarboxylic acid and alicyclic dicarboxylic acid which have an aromatic ring are mentioned, In particular, aromatic with 8-36 carbon atoms from a viewpoint of reduction of a YI value and total light transmittance. At least one compound selected from the group consisting of dicarboxylic acid and alicyclic dicarboxylic acid having 6 to 34 carbon atoms is preferable. Specifically, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 1,4-naphthalene Dicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-sulfonylbisbenzoic acid, 3,4'- Sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4- Carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-dimethyl-4,4'-ratio Phenyldicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene, 4,4'-bis (4-carboxyphenoxy) biphenyl, 4,4'-bis (3-carboxyphenoxy) biphenyl, 3,4 '-Bis (4-carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphene Biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3-carboxyphenoxy) biphenyl, 4,4'-bis (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,4'-bis (4-carboxyphenoxy) -p-terphenyl, 3,3'-bis (4-carboxyphenoxy) -p-terphenyl, 3,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,3'-bis (4-carboxyphenoxy) -m-terphenyl , 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,4'-bis (3-carboxyphenoxy C) -p-terphenyl, 3,3'-bis (3-carboxyphenoxy) -p-terphenyl, 3,4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,3 ' -Bis (3-carboxyphenoxy) -m-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4, 5-aminoisoprop described in 4'-benzophenonedicarboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, and international publication 2005/068535 pamphlet. Deoxidation derivatives; When these dicarboxylic acids are actually copolymerized to a polymer, you may use it in the form of the acid chloride body or active ester body derived from thionyl chloride etc.

Among these, terephthalic acid is especially preferable from a viewpoint of reducing YI value and improving Tg. When dicarboxylic acid is used instead of tetracarboxylic acid, it is preferable from a chemical-resistant viewpoint that dicarboxylic acid is 50 mol% or less with respect to the total number of moles which combined dicarboxylic acid and tetracarboxylic acid.

<Diamine>

Diamine contained in a polymerization component contains the diamine represented by General formula (1). The diamine represented by General formula (1) can comprise the diamine derived site | part of the unit 1 mentioned later, for example. In the resin precursor, the site | part derived from the diamine represented by General formula (1) is suitable for the yellowness of a polyimide film, low birefringence, the improvement of total light transmittance, the fall of the residual stress which arises between an inorganic film, high It is preferable that it is 20 mol% or more of a total diamine derived site | part from a viewpoint of obtaining Tg and high breaking strength, It is more preferable that it is 50 mol% or more, It is further more preferable that it is 80 mol% or more.

Moreover, diamine can contain the diamine (henceforth simply a silicon containing diamine hereafter) which has a bivalent silicon containing group of silicon number 2-100. As the silicon-containing diamine, for example, the following general formula (9):

[Formula 13]

{In formula, _{two or} more R <_2> is respectively independently a C3-C20 divalent aliphatic hydrocarbon or a divalent aromatic group, R <_3> and R <_4> is respectively independently C1-C20 monovalent It is an organic group, and l is an integer of 3-50.} The diamino (poly) siloxane represented by the} is suitable. Such diamine can comprise the unit 2 mentioned later, for example.

As a preferable structure of R <_{2> in} the said General formula (9), a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, etc. are mentioned. Moreover, as a suitable example with respect to R <_3> and R <_4> in the said General formula (9), a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, etc. are mentioned, It is especially preferable that at least one part is a phenyl group.

As a compound represented by the said General formula (9), specifically, both terminal amine modified methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd. make: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average molecular weight 1300)) , Both terminal amino-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-161A (number average molecular weight 1600), X22-161B (number average molecular weight 3000), KF8021 (number average molecular weight 4400), manufactured by Tore Dow Corning: BY16-835U (water (Average molecular weight 900) Tosso Co., Ltd. product: Sila plain FM3311 (number average molecular weight 1000)) etc. are mentioned. Among them, both terminal amine-modified methylphenylsilicone oils are particularly preferred from the viewpoint of improving chemical resistance and improving Tg.

In addition, diamines are 2,2'-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB), 4,4'- (or 3,4'-, 3,3'-, 2,4'- ) Diaminodiphenylether, 4,4'- (or 3,3'-) diaminodiphenylsulfone, 4,4'- (or 3,3'-) diaminodiphenylsulfide, 4,4 ' -Benzophenonediamine, 3,3'-benzophenonediamine, 4,4'-di (4-aminophenoxy) phenylsulfone, 4,4'-di (3-aminophenoxy) phenylsulfone, 4,4 ' -Bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis {4- (4 -Aminophenoxy) phenyl} propane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, 2,2 ', 6,6'-tetramethyl-4,4'-diaminobiphenyl, 2,2', 6,6'-tetratrifluoromethyl-4,4'-diaminobiphenyl, bis {(4 -Aminophenyl) -2-propyl} 1,4-benzene, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-aminophenoxyphenyl) fluorene, 3,3'- Dimethylbenzidine 2,6-diaminopyridine, 2,4-diaminopyridine, bis (4-aminophenyl-2-propyl) -1,4, such as 3,3'-dimethoxybenzidine and 3,5-diaminobenzoic acid -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'-bis (3-aminophenyl) Hexafluoropropane (3,3'-6F), and 2,2'-bis (4-aminophenyl) hexafluoropropane (4,4'-6F) and at least one member selected from the group consisting of You may also These diamine can comprise the diamine derived site | part of the unit 3 mentioned later. Among these, 1,4-cyclohexanediamine and TFMB are most preferable from a viewpoint of the fall of yellowness, the fall of CTE, and the fall of YI value.

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

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

[Formula 14]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, X <_{1> which} may exist in multiple numbers each independently represents C4-C20. 32 is a tetravalent organic group, and n is an integer of 1-100.}

Has a structure represented by

The unit 2 has the following general formula (5):

[Formula 15]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, and _{two or} more R <_2> is respectively independently C3-C20 Is a divalent aliphatic hydrocarbon or a divalent aromatic group, R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and a plurality of each of X _{2, which} may be present, are each independently 4 to 4 carbon atoms. 32 is a tetravalent organic group, l is an integer of 3-50, and m is an integer of 1-100.} The structure represented by the following or general formula (6):

[Formula 16]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, and two or more R <_3> and R <_4> respectively independently represents carbon number R <_{8> which} is a 1-20 monovalent organic group, two or more R <_8> is respectively independently a C3-C20 trivalent aliphatic hydrocarbon or a trivalent aromatic group, p is an integer of 1-100, and q is It is an integer of 3-50.}, Or both of the structure represented by the said General formula (5), and the structure represented by the said General formula (6).

In General Formulas (4) and (6), the diamine-derived site is, for example, 4,4- (diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone, and 3,3- It may be derived from one or more diamine selected from the group consisting of (diaminodiphenyl) sulfone. In the general formulas (4) and (5), the acid anhydride-derived site is an acid dianhydride 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) and an acid dianhydride. The diamine derived site | part in the structure represented by General formula (5) is derived from the diamino (poly) siloxane represented by General formula (9).

Unit 1 and unit 2 are, in terms of heat resistance, reduction of YI value and total light transmittance,

A site derived from one or more selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA);

4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid 2 Anhydride (CHDA), 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis (trimelitic acid monoester acid anhydride) (TAHQ), and Sites derived from one or more selected from the group consisting of 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF)

The site of the combination is based on the total amount of the acid 2 anhydride derived sites of Unit 1 and Unit 2, preferably in an amount of at least 60 mol%, more preferably at least 65 mol%, even more preferably at least 70 mol%. Included in quantity.

In the resin precursor which concerns on this embodiment, it is preferable from the viewpoint of the reduction of a YI value, the reduction of birefringence, and Tg improvement that the total mass of unit 1 and unit 2 is 30 mass% or more on the basis of the total mass of a resin precursor. Moreover, 70 mass% or more is preferable from a viewpoint of reduction of a birefringence. Most preferably, it is 100 mass%.

Moreover, the resin precursor which concerns on this embodiment is following General formula (7): in the range which does not impair performance as needed.

[Formula 17]

{In formula, two or more R <_1> is a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group each independently, X <_{3> which} may exist in multiple numbers each independently represents C4-C20. X _{4 which} may be a 32-valent divalent organic group, and which may exist in multiple numbers each independently is a C4-C32 tetravalent organic group, and t is an integer of 1-100.} The unit 3 which has a structure represented by You may further contain it.

Unit 3 is a structure which is a site | part derived from diamine other than the compound chosen from the group which a diamine derived site | part consists of 4,4-DAS, 3,4-DAS, 3,3-DAS, and a silicon containing diamine.

In unit 3, R ₁ is preferably a hydrogen atom. X ₃ is preferably a divalent aromatic group or alicyclic group from the viewpoint of heat resistance, reduction of YI value and total light transmittance. X ₄ is preferably a divalent aromatic group or alicyclic group from the viewpoint of heat resistance, reduction of YI value and total light transmittance. Especially, it is preferable that X <_3> is a residue which is a structure remove | excluding the amino group from 2,2'-bis (trifluoromethyl) benzidine. The organic groups X ₁ , X ₂ and X ₄ may be the same as or different from each other.

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

The resin precursor which concerns on this embodiment is resin obtained by heat-hardening the resin precursor in 300 degreeC-500 degreeC in inert atmosphere (for example, atmosphere of nitrogen or argon), or this resin precursor at 350 degreeC in inert atmosphere. Resin obtained by heat-hardening has at least one glass transition temperature in the area | region of -150 degreeC-0 degreeC, and at least one glass transition temperature of the area | region of 150 degreeC-380 degreeC, and is in the area | region larger than 0 degreeC and less than 150 degreeC It is preferable not to have a glass transition temperature. It is preferable that a glass transition temperature exists in the area | region of -150 degreeC-0 degreeC, and the area | region of 150 degreeC-380 degreeC from a viewpoint of making the balance of residual stress and total light transmittance favorable. 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 even more preferably in the range of 250 to 380 ° C. It is advantageous in the formation of such a resin precursor that the resin precursor has blocks 1 and 2 described later.

It is preferable that the resin precursor which concerns on this embodiment is comprised from the block 1 which mainly uses the unit 1, and the block 2 which mainly contains the unit 2 from a viewpoint of improving heat resistance. In addition, the resin precursor may contain the unit 3 mentioned above in block 1. These blocks may be bonded alternately in the polymer chain or may be bonded in permutation.

Block 1 mentioned above contributes to expressing Tg in the range of 150-380 degreeC in the polyimide obtained by heat-hardening the resin precursor of this embodiment. Therefore, although block 1 is preferable to be a block which consists only of the repeat of unit 1 mentioned above, in the range which can express target Tg, it does not exclude including unit 3 other than the unit 1.

Similarly, the block 2 mentioned above contributes to expressing Tg in the range of -150-0 degreeC in the polyimide obtained by heat-hardening the resin precursor of this embodiment. Therefore, block 2 is preferably a block composed of only the repetition of unit 2 described above, but does not exclude the inclusion of units other than the unit 2 in a range capable of expressing the target Tg.

In the resin precursors having blocks 1 and 2, the average number of repetitions of units 1 and 3 in block 1 is preferably 2 to 500, more preferably 5 to 300, and more preferably 10 to 200. Is most preferred. Moreover, as for the repeating number of the unit 2 in the block 2, 1.1-300 are preferable on average per molecule, 1.1-200 are more preferable, 1.2-100 are the most preferable. Since the sum of the repeating numbers of the unit 1 and the unit 3 in the block 1 is 500 or less, and the repeating number of the unit 2 in the block 2 is 300 or less, the solubility to the solvent of the resin precursor becomes favorable, and it is preferable. .

The ratio (hereinafter also referred to as unit ratio) defined as the value obtained by dividing the sum of the repetition numbers of the unit 1 and the unit 3 in the block 1 by the repetition number of the unit 2 in the block 2 is referred to as the type and molecular weight of the raw material to be used. Although it depends also, it is preferable that it is 0.5-100, and it is more preferable that it is 10-50. As mentioned above, the polyimide which is the hardened | cured material of the resin precursor which has block 1 and the block 2 has the glass transition temperature originating in block 1 in area | region A of 150 degreeC-380 degreeC, and-the glass transition temperature originating in block 2 is-. It can have the advantage that it has in the area | region B of 150 degreeC-0 degreeC, and does not have a glass transition temperature in the area | region C between this area | region A and this area | region B. When the value of the unit ratio mentioned above is 0.5 or more, it becomes preferable that the heat resistance of the polyimide resin after hardening is sufficient. Moreover, when it is 100 or less, since residual stress can be made low, it is preferable.

On the other hand, when using a high molecular weight silicone compound (specifically, a silicone compound with an average molecular weight of 3000 or more) as a silicon-group containing compound in a polymerization component, even if it does not form a block copolymer as mentioned above, the polyimide obtained is high Low residual stress with the inorganic film can be expressed while maintaining the glass transition temperature. This is because, according to the high molecular weight silicone compound, the silicon unit itself has a long-chain siloxane structure, and is considered to have the same function as the block structure. In the case where the silicon compound has a high molecular weight, the functional group concentration is lowered, and therefore the number of moles added can express at least the high oil transition temperature and the low residual stress.

For example, when a high molecular weight silicone compound is a diamine, the resin precursor is an air of unit 1 of general formula (4) derived from (diaminodiphenyl) sulfone and unit 2 of general formula (5) derived from silicone diamine. In addition to the coalescence, a polyimide precursor mixture, ie a blend, is produced in which the polyimide precursor of unit 1 alone (i.e., unit 2 is not copolymerized) is present.

Therefore, this disclosure also includes the precursor mixture containing the resin precursor of this embodiment mentioned above and an additional resin precursor (for example, the polyimide precursor of the said unit 1 alone). Here, as a specific example of the polyimide precursor of this unit 1 alone, following General formula (8):

[Formula 18]

{In formula, X <_{3> which} may exist in multiple numbers is respectively independently a C4-C32 tetravalent organic group, and two or more R <_1> represents a hydrogen atom and a C1-C20 monovalent aliphatic hydrocarbon each independently. It is group or a monovalent aromatic group, and r is an integer of 1-100.} The resin precursor which has a structure shown by the following is mentioned.

On the other hand, in the case where the high molecular weight silicone compound is other than diamine, for example, in General Formula (3), L ₁ , L ₂ , and L ₃ are each independently an acid anhydride group, a carboxyl group, or an acid ester group. , An acid halide group, a hydroxyl group, an epoxy group, or a mercapto group.

In the resin precursor which concerns on this embodiment, when a superposition | polymerization component contains a high molecular weight silicone compound, the polyimide which is the hardened | cured material of this resin precursor maintains the glass transition temperature in the area | region of 150 degreeC-380 degreeC high, The peculiar characteristic that the residual stress with an inorganic film can be remarkably reduced can be achieved.

It is preferable that the number average molecular weights of the resin precursor which concerns on this embodiment are 3000-1 million, More preferably, it is 5000-50000, More preferably, it is 7000-300000, Especially preferably, it is 10000-250000. It is preferable that the molecular weight is 3000 or more from the viewpoint of satisfactorily obtaining heat resistance and strength (for example, elongation), and 1 million or less is immersed in the desired film thickness during processing such as the viewpoint of obtaining good solubility in a solvent and coating. It is preferable at the point which can apply | coat without this. From a viewpoint of obtaining high mechanical elongation, it is preferable that molecular weight is 50000 or more. In this disclosure, a number average molecular weight is a value calculated | required in standard polystyrene conversion using gel permeation chromatography.

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

The resin precursor of this embodiment has the glass transition temperature of 150 degreeC-380 degreeC on the high temperature side as heat resistance which can endure the display manufacturing process provided with TFT element apparatus on a colorless transparent polyimide substrate, and also has an inorganic film. Residual stress in between can form the polyimide resin of 25 Mpa or less with a 10 micrometer film thickness. Moreover, in a more suitable aspect, the resin precursor can form the polyimide resin whose residual stress between an inorganic film and a glass transition temperature of 240 degreeC-380 degreeC is 20 Mpa or less with a 10 micrometer film thickness. In a polyimide resin, when a glass transition temperature exists at -150-0 degreeC, since this temperature is room temperature or less, it does not affect the heat resistance required by an actual display manufacturing process.

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

After developing the solution obtained by melt | dissolving a resin precursor in a solvent (for example, N-methyl- 2-pyrrolidone) on the surface of a support body, the solution is 300-500 degreeC (for example, 350 degreeC) in nitrogen atmosphere. In the resin obtained by imidating the resin precursor by heating at (for example, 1 hour), the yellowness in the 20 μm film thickness is 7 or less.

After developing the solution obtained by melt | dissolving a resin precursor in a solvent (for example, N-methyl- 2-pyrrolidone) on the surface of a support body, the solution is 300-500 degreeC (for example, 350 degreeC) in nitrogen atmosphere. In the resin obtained by imidating the resin precursor by heating (for example, 1 hour) in the resin), the residual stress at 10 μm film thickness is 25 MPa or less.

<Production of Resin Precursor>

Next, the synthesis | combining method of the resin precursor which concerns on this embodiment is demonstrated. For example, when the resin precursor which concerns on this embodiment is comprised from two blocks like block 1 and block 2 mentioned above, the polyimide precursor corresponding to each block is prepared separately, and both are mixed after that. And the resin precursor which concerns on this embodiment can be obtained by providing to a condensation reaction. When the terminal group of the polyimide precursor of one block is made into carboxylic acid so that both blocks may be provided to a condensation reaction, the terminal group of the polyimide precursor of the other block shall be an amino group, respectively. Molar ratio of tetracarboxylic dianhydride and diamine, for example. In this method, a polyimide precursor having more preferable complete blockability can be synthesized.

On the other hand, when tetracarboxylic dianhydride which is a polymerization raw material is common between block 1 and block 2, and uses aromatic diamine as a raw material of block 1, and uses highly reactive silicon containing diamine as a raw material of block 2, The synthesis method using the reactivity difference of both diamine may become possible. For example, the polyimide precursor which has a certain blockiness can be manufactured by adding aromatic diamine and silicon containing diamine simultaneously to the tetracarboxylic dianhydride prepared previously, and using for a condensation reaction. In this method, a blocky polyimide precursor having perfect blockability cannot be synthesized, but a polyimide precursor having blockability can be synthesized. In the polyimide resin after heat-hardening, the thing with blockiness here is that the glass transition temperature corresponding to each block is observed, for example, the polyimide resin has 4, in each of the area | region A and area | region B mentioned above. Polycondensation of at least one selected from the group consisting of 4- (diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone and 3,3- (diaminodiphenyl) sulfone and tetracarboxylic anhydride It means what shows the glass transition temperature of the block 1 derived from copolymerization, and the glass transition temperature of the block 2 derived from the polycondensate of silicon containing diamine and tetracarboxylic anhydride, respectively.

As described above, the resin precursor according to the present embodiment has a blockiness such that the polyimide resin obtained by heating and curing the resin precursor is such that the glass transition temperature is confirmed in the region A on the high temperature side and the region B on the low temperature side, respectively. Although advantageous to have, this advantage can be obtained even if the polyimide resin does not have complete blockability. Moreover, the above-mentioned advantage by the resin precursor which has blocks 1 and 2 is acquired even if it contains units other than block 1 and block 2, unless a glass transition temperature is confirmed in the area | region C between the area | region A and this area | region B. It is possible.

Moreover, by adding N, N-dimethylformamide dimethylacetal or N, N-dimethylformamide diethyl acetal to the polyamic acid as mentioned above and heating, esterifying a part or all of carboxylic acid, The viscosity stability at the time of room temperature storage of the solution containing a resin precursor and a solvent can also be improved. These ester-modified polyamic acids, in addition, after reacting the tetracarboxylic anhydride mentioned above with 1 equivalent of monohydric alcohol with respect to an acid anhydride group previously, dehydrating condensing agents, such as thionyl chloride and dicyclohexyl carbodiimide, It can also be obtained by condensation reaction with diamine after reacting with.

<Resin composition>

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

In a more preferred embodiment, the resin composition is prepared as a polyamic acid solution containing a polyamic acid and a solvent, which is a solution of a carboxylic acid component and a diamine in a solvent such as an organic solvent and reacted. can do. Here, although the conditions at the time of reaction are not specifically limited, For example, reaction temperature is -20-150 degreeC and reaction time is 2 to 48 hours. In order to fully advance the reaction of the silicon group-containing compound, heating at about 120 ° C. for about 30 minutes is preferable. Moreover, at the time of reaction, it is preferable that it is inert atmosphere, such as argon and nitrogen.

Moreover, a solvent will not be specifically limited if it is a solvent in which a polyamic acid is dissolved. As known reaction solvents, dimethylene glycol dimethyl ether (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide ( DMSO), acetone, diethyl acetate, ecamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and ecamide B100 (brand name: manufactured by Idemitsu Kosan Co., Ltd.) are useful. Among them, NMP, DMAc, ecamide M100 and ecamide B100 are preferable. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform, or a low absorbing solvent such as γ-butyrolactone may be used.

Moreover, in the resin composition of this invention, when the obtained polyimide forms elements, such as TFT, in order to provide sufficient adhesiveness with a support body, 0.01-2 mass% of an alkoxysilane compound is contained with respect to 100 mass% of resin precursors. The composition to say is preferable.

When content of an alkoxysilane compound is 0.01 mass% or more with respect to 100 mass% of resin precursors, favorable adhesiveness with a support body can be obtained and it is a viewpoint of the storage stability of a resin composition that content of an alkoxysilane compound is 2 mass% or less. Preferred at As for content of an alkoxysilane compound, it is more preferable that it is 0.02-2 mass% with respect to a resin precursor, It is still more preferable that it is 0.05-1 mass%, It is still more preferable that it is 0.05-0.5 mass%, 0.1-0.5 mass% Is particularly preferred.

Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and phenyltrimethoxysilane , γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyl Trimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, (gamma) -aminobutyl tributoxysilane etc. are mentioned, These may use together 2 or more types.

After manufacturing the varnish mentioned above, you may dehydrate | dehydrate a part of polymer so that a polymer may not precipitate by heating a solution at 130-200 degreeC for 5 minutes-2 hours. By controlling temperature and time, the imidation ratio can be controlled. By partial imidation, the viscosity stability at the time of room temperature storage of a resin precursor solution can be improved. As an imidation range, 5%-70% are preferable from a viewpoint of the solubility of the resin precursor to a solution, and the storage stability of a solution.

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

Resin obtained by developing the resin composition on the surface of a support body, and imidizing the resin precursor contained in a resin composition by heating this resin composition at 300 degreeC-500 degreeC in nitrogen atmosphere (or by heating at 350 degreeC in nitrogen atmosphere). The yellowness in the 20 micrometer film thickness which is shown is 7 or less.

Resin obtained by developing the resin composition on the surface of a support body, and imidizing the resin precursor contained in a resin composition by heating this resin composition at 300 degreeC-500 degreeC in nitrogen atmosphere (or by heating at 350 degreeC in nitrogen atmosphere). Residual stress in the 10 micrometer film thickness shown by is 25 Mpa or less.

<Resin film>

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

Moreover, the other aspect of this invention is a process of developing the above-mentioned resin composition on the surface of a support body,

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

Process of peeling this resin film from the support body

It provides a method for producing a resin film comprising a.

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

Here, although a support body is an inorganic substrate like glass substrates, such as an alkali free glass substrate, it is not specifically limited, for example.

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

Here, as a development method, the well-known coating method of a spin coat, a slit coat, and a blade coat is mentioned, for example. In addition, after heat-processing a polyamic-acid solution on a contact bonding layer, heat processing heat-processes for 1 to 300 minutes at the temperature of 300 degrees C or less mainly for the purpose of a desolvent, and 300 degreeC-in inert atmosphere, such as nitrogen, It heat-processes for 1 minute-300 minutes at the temperature of 550 degreeC, and makes a resin precursor polyimide. When manufacturing a conventional colorless transparent polyimide film, it is necessary to manage the oxygen concentration in oven in 100 ppm or less from a viewpoint of reduction of a YI value and total light transmittance, but according to the resin precursor in this embodiment, For example, a control 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.

Moreover, the thickness of the resin film which concerns on this embodiment is not specifically limited, It is preferable that it is the range of 10-200 micrometers, More preferably, it is 10-50 micrometers.

It is preferable that the yellowness in 20 micrometer film thickness of the resin film which concerns on this embodiment is 7 or less. Moreover, it is preferable that residual stress is 25 Mpa or less with a 10 micrometer film thickness. In particular, it is more preferable that yellowness in 20 micrometer film thickness is 7 or less, and residual stress is 25 Mpa or less in 10 micrometer film thickness. Such a characteristic is satisfactorily realized by, for example, imidizing the resin precursor of the present disclosure at 300 ° C to 500 ° C, more particularly at 350 ° C under a nitrogen atmosphere.

<Laminated body>

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

Moreover, another aspect of this invention is the process of developing the above-mentioned resin composition on the surface of a support body,

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

It provides a manufacturing method of a laminate comprising.

Such a laminated body can be manufactured by not peeling from the support body the resin film formed like the manufacturing method of the above-mentioned resin film, for example.

This laminated body is used for manufacture of a flexible device, for example. More specifically, a semiconductor device is formed on a polyimide film, a support body is peeled after that, and the flexible device provided with the flexible transparent substrate which consists of a polyimide film can be obtained.

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

As explained above, the resin precursor which concerns on this embodiment can form the resin film which is not cloudy, without requiring a special solvent combination by having a specific structure. Moreover, the yellowness (YI value) and total light transmittance of the obtained resin film are little dependent on oxygen concentration at the time of curing. Moreover, the residual stress generated between the resin film and the inorganic film is low, has a practical glass transition temperature that can withstand the TFT manufacturing process, is excellent in mechanical properties, and has chemical resistance that can withstand the photolithography process. Therefore, this resin precursor is suitable for use in the transparent substrate of a flexible display.

In more detail, when forming a flexible display, using a glass substrate as a support body, a flexible substrate is formed on it, and TFT etc. are formed on it. Although the process of forming a TFT on a substrate is typically performed at a wide range of temperatures of 150 to 650 ° C, in order to actually achieve desired performance, the TFT is mainly used at around 250 ° C to 350 ° C, using an inorganic material. -IGZO (InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si-TFT) is formed.

At this time, if the residual stress generated in the flexible substrate and the polyimide film is high, when expanded in a high-temperature TFT process and then contracted at room temperature cooling, warping or damage of the glass substrate, peeling from the glass substrate of the flexible substrate, etc. Problem occurs. Generally, since the thermal expansion coefficient of a glass substrate is small compared with resin, residual stress generate | occur | produces with a flexible substrate. In consideration of this point, it is preferable that the resin film which concerns on this embodiment is 25 Mpa or less in the residual stress which arises between a resin film and glass on the basis of 10 micrometers in thickness of a film.

Moreover, when the resin film which concerns on this embodiment has a yellowness of 7 or less on the basis of 20 micrometers in thickness of a film, and measures the transmittance with an ultraviolet spectrophotometer on the basis of 20 micrometers in thickness of a film, It is preferable that the transmittance | permeability in 550 nm is 85% or more. Moreover, the one with less oxygen concentration dependence in the oven used when manufacturing a thermosetting film is advantageous in obtaining a resin film with a low YI value stably, and the YI value of a thermosetting film is the oxygen concentration of 500 ppm or less. It is preferable that this is stable.

Moreover, since the resin film which concerns on this embodiment is excellent in breaking strength when handling a flexible board | substrate, it is more preferable that mechanical elongation is 30% or more on the basis of 20 micrometers in thickness from a viewpoint of improving a yield. .

Moreover, in the resin film which concerns on this embodiment, in order that softening of a resin substrate does not generate | occur | produce at the temperature which manufactures TFT element, it is preferable that glass transition temperature is 250 degreeC or more.

Moreover, it is preferable that the resin film which concerns on this embodiment is equipped with the chemical resistance which can endure the photoresist peeling liquid in the photolithography process used when manufacturing TFT element.

In addition, there are two types of light extraction methods of the flexible display, a top emission method for taking out light from the front side of the TFT element and a bottom emission method for taking out light from the back side. In the top emission method, since the TFT element does not interfere, the aperture ratio is easily increased. The bottom emission method is easy to align and easy to manufacture. If the TFT element is transparent, it is possible to improve the aperture ratio also in the bottom emission method, and therefore, it is expected that a bottom emission method that is easy to manufacture is adopted in a large organic EL flexible display. When using a resin substrate for a colorless transparent resin substrate used for a bottom emission method, since the resin substrate comes to the visual recognition side, it is low in optical thickness isotropic, ie, the retardation (Rth) of the thickness direction derived from birefringence is low. It is required from the point of view of improvement. Moreover, when using for a top emission system, although it is not required that Rth is low, the material with low Rth is considered to be preferable from a viewpoint that it can be used for both systems. Specifically, 200 nm or less is preferable based on the thickness of 20 micrometers of a film, More preferably, 90 nm or less is preferable, More preferably, 80 nm or less is preferable, Especially preferably, it is 50 nm or less to be. When Rth is 100 nm or less and 90 nm or less, it satisfies not only the top emission type transparent display substrate but also the performance for applying to the bottom emission type flexible display substrate and the touch panel electrode substrate. .

Another aspect of the present invention provides a polyimide resin film having a Rth of 20 to 90 nm in a thickness of 20 µm as a polyimide resin film used for producing a display substrate.

Moreover, another aspect of this invention is the process of developing the resin composition containing a polyimide precursor on the surface of a support body,

Heating the support and the resin composition to imidize the polyimide precursor to form the polyimide resin film described above;

Forming an element on the polyimide resin film;

Process of peeling the polyimide resin film in which the element was formed from the support body

It provides a method of manufacturing a display substrate comprising a.

The resin film which concerns on the said physical property which satisfy | fills the said physical property is used suitably as a colorless transparent board | substrate for the use limited by the yellow which the existing polyimide film has, especially a flexible display. Furthermore, for example, a diffuser sheet and a coating film (for example, an interlayer of a TFT-LCD, a gate insulating film, and a liquid crystal aligning film) in a protective film or a TFT-LCD, an ITO substrate for a touch panel, and a cover glass replacement resin for a smartphone Colorless transparency, such as a board | substrate, can also be used also in the field | area where low birefringence is calculated | required. When applying the polyimide which concerns on this embodiment as a liquid crystal aligning film, it contributes to the increase of aperture ratio, and manufacture of high contrast ratio TFT-LCD is possible.

The resin film and laminated body manufactured using the resin precursor which concerns on this embodiment can be used suitably especially as a board | substrate for manufacture of a semiconductor insulating film, TFT-LCD insulating film, an electrode protective film, and a flexible device, for example. . Here, with a flexible device, a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, flexible illumination, and a flexible battery are mentioned, for example.

Example

Hereinafter, although this invention is demonstrated in detail based on an Example, these are described for description, and the scope of the present invention is not limited to the following Example.

The various evaluations in an Example and a comparative example were performed 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 (made by Wako Pure Chemical, Ltd., purity 99.5%) using N, N-dimethylformamide (made by Wako Pure Chemical, Ltd., for high-speed liquid chromatograph) before measurement ) And 63.2 mmol / L phosphoric acid (made by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) were used. In addition, the calibration curve for calculating a weight average molecular weight was created using standard polystyrene (made by Tosoh Corporation).

Column: Shodex KD-806M (Showa Denko Corporation)

Flow rate: 1.0 ml / min

Column temperature: 40 degrees Celsius

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

Detector: RI-2031Plus (RI: differential refractometer, the JASCO company make)

        UV-2075Plus (UV-VIS: Ultraviolet Visible Light Absorber, manufactured by JASCO Corporation)

(Silicone group-containing monomer concentration)

The silicon group containing monomer concentration was computed from the following formula using the mass of each of the silicon group containing monomer, polyhydric carboxylic acid or its derivative (s), diamine compound, which are used when synthesize | combining a resin precursor.

Silicon group-containing monomer concentration (%) = silicon group-containing monomer mass / (silicon group-containing monomer mass + polyhydric carboxylic acid or derivative thereof + mass of diamine compound) x 100

(Manufacture of Laminate and Isolation Film)

The resin composition was applied to an alkali free glass substrate (thickness 0.7 mm) with a bar coater, and leveled at room temperature for 5 minutes to 10 minutes, and a vertical curing oven (manufactured by Koyo Lindberg, model name VF-2000B) The mixture was heated at 140 ° C. for 60 minutes, and further heated at 350 ° C. 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 oxygen concentration dependence of the YI value and the total light transmittance was investigated. The film thickness of the resin composition of the laminated body was 20 micrometers. After curing at 350 ° 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. Evaluation other than the following yellowness and total light transmittance adjusted the oxygen concentration in hot air oven to 100 ppm, and used the resin film which cured at 350 degreeC for 60 minutes as a sample.

(Evaluation of tensile elongation)

A resin film having a sample length of 5 × 50 mm and a thickness of 20 μm cured at 350 ° C. was pulled at a speed of 100 mm / min using a tensile tester (manufactured by A & D Co., Ltd .: RTG-1210) to measure the elongation. It was.

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

The oxygen concentration in the oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and a resin film having a thickness of 20 μm, which was cured at 350 ° C., was used as a D65 light source by Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600). The yellowness (YI value) and total light transmittance were measured.

(Evaluation of Thickness Direction Retardation (Rth))

The 20-micrometer-thick resin film cured at 350 degreeC was measured using the retardation birefringence measuring apparatus (Oji Measurement Instruments Co., Ltd. make, KOBRA-WR). The wavelength of the measurement light was 589 nm.

(Evaluation of Glass Transition Temperature, Linear Expansion Coefficient)

Regarding the measurement of the glass transition temperature (referred to as Tg (1)) and the linear expansion coefficient (CTE) in the room temperature area or more, a resin film having a sample length of 5 × 50 mm and a thickness of 20 μm, cured at 350 ° C., By using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation, load 5 g, temperature increase rate of 10 ° C / min, nitrogen atmosphere (flow rate 20 ml / min), temperature of 50 to 450 ° C The test piece elongation in the range was measured, the inflection point was calculated | required as glass transition temperature, and the CTE of the heat resistant resin film of 100-250 degreeC was calculated | required.

Since it is impossible with the said method about the measurement of the glass transition temperature (it is called Tg (2)) below room temperature region, the said resin film is a dynamic viscoelasticity measuring apparatus in the range of -150 degreeC-400 degreeC (Orientech) The inflection point in the temperature range below room temperature of E prime was measured by RHEOVIBRON MODEL RHEO-1021), and the inflection point was calculated | required as glass transition temperature in low temperature.

(Evaluation of Residual Stress)

The resin composition was applied by a bar coater onto a 6-inch silicon wafer having a thickness of 625 µm ± 25 µm in which the "warping amount" was measured in advance using a residual stress measuring apparatus (manufactured by Tencor Corporation, model name FLX-2320). After prebaking at 140 ° C. for 60 minutes, a heat curing treatment was performed at 350 ° C. for 1 hour in a nitrogen atmosphere, using a vertical cure (manufactured by Koyo Lindberg, model name VF-2000B), and the film after curing. A silicon wafer with a resin film having a thickness of 10 μm was prepared. The amount of warpage of this wafer was measured using the above-described residual stress measuring apparatus, and the residual stress generated between the silicon wafer and the resin film was evaluated.

(Evaluation of chemical resistance test)

The resin film piece of 20 micrometers in thickness which was cured at 350 degreeC was immersed in the NMP layer of room temperature, pulled up every 10 minutes, and wash | cleaned with ion-exchange water, and then the film surface was observed under a microscope, and a crack was made to the surface of a thermosetting film. Evaluation of the time to be formed was performed at 300 minute intervals at 10 minute intervals.

Example 1

To a 3 L separable flask equipped with a stirring rod equipped with an oil bath, 1000 g of NMP was added while introducing nitrogen gas, and 232.4 g of 3,3- (diaminodiphenyl) sulfone (prescribed as diamine 1) was added. It added while stirring, 218.12g of pyromellitic dianhydrides (it prescribes | regulated as tetracarboxylic anhydride 1) were then added, and it stirred at room temperature for 30 minutes. After heating up this at 50 degreeC and stirring for 12 hours, NMP 105.6g of both terminal amine modified methylphenyl silicone oils (made by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (prescribed by silicon-group containing diamine) It melt | dissolved in 298g, was added dropwise using the dropping funnel. After heating up at 80 degreeC and stirring for 1 hour, the oil bath was removed and returned to room temperature, and the transparent NMP solution (henceforth a varnish) of polyamic acid was obtained. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1. Moreover, the test result of the film cured at 350 degreeC is shown in Table 4.

[Examples 2 to 33 and 49 to 58]

In the same manner as in Example 1, the diamine 1, the tetracarboxylic anhydride 1, the type of silicon group-containing diamine, and their added mass were changed to those shown in Table 1, respectively, and the same operation as in Example 1 was carried out to give the varnish. Got it. In addition, the NMP addition amount shown in Table 1 and Table 2 shows the total amount of NMP finally contained in a varnish, and is the mass containing 298 g of NMP which dilutes a silicon-group containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1, Table 2, and Table 7, respectively. Moreover, the test result of the film cured at 350 degreeC is shown to Table 4, Table 5, and Table 8, respectively. The formal compound name of the short compound name shown in Table 1-Table 6 is described below.

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

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

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

PMDA: pyromellitic dianhydride

ODPA: 4,4'- oxydiphthalic acid dianhydride

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

BPDA: 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride

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

DSDA: 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride

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

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

TAHQ: 4,4'-biphenyl bis (trimelitic acid monoester acid anhydride)

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

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

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

FM3311: Both terminal amine-modified dimethyl silicone oils (Cyraplane FM3311 (number average molecular weight 1000) by Chisso Corp.)

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 stirring rod equipped with an oil bath, 1274 g of NMP was added thereto, and 4,4'-oxydiphthalic acid dianhydride (hereinafter referred to as ODPA) (tetracar) 105.6 g of both terminal amine-modified methylphenylsilicone oils (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (prescribed as a silicon group-containing diamine) are added while stirring. The thing dissolved in 298 g of NMP was dripped using the dropping 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) are added while stirring, followed by 3,3- 116.2 g of DAS was added with stirring, and it stirred at room temperature for 1 hour. Then, it heated at 50 degreeC, added 147.1g of BPDA (it defines with tetracarboxylic anhydride 2), and stirred for 12 hours. After heating up this to 80 degreeC and stirring for 4 hours, the oil bath was removed and returned to room temperature, and the transparent NMP solution (it is also described as varnish below) was obtained. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2. Moreover, the test result of the film cured at 350 degreeC is shown in Table 5.

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

In the same manner as in Example 34, the types of diamine 1, diamine 2, tetracarboxylic anhydride 1, tetracarboxylic anhydride 2, and their added mass were changed to those shown in Table 2, respectively, and the same operation as in Example 34 was performed. Was carried out to obtain a varnish. In addition, NMP addition amount shown in Table 2 shows the total amount of NMP finally contained in a varnish, and is the mass containing 298 g of NMP which dilutes a silicon-group containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. Moreover, the test result of the film cured at 350 degreeC is shown in Table 5, respectively.

Example 36

1196 g of N-methylpyrrolidone (hereinafter referred to as NMP) was added to a 3 L separable flask equipped with a stirring rod equipped with an oil bath while introducing nitrogen gas, and 3,3- (diaminodi 232.4 g of phenyl) sulfone (prescribed as diamine 1) were added with stirring, and after heating to 50 degreeC, 147.1 g of BPDA (prescribed as tetracarboxylic anhydride 1) was added and stirred for 30 minutes. Subsequently, after adding 155.1 g of ODPA (prescribed as tetracarboxylic anhydride 2) and stirring for 8 hours, both terminal amine-modified methylphenyl silicone oils (Shin-Etsu Chemical Co., Ltd. make: X22-1660B-3 (number average molecular weight 4400)) ( 105.6 g of NMP 298 g was dissolved, and it was added dropwise by using a dropping funnel. After heating up at 80 degreeC and stirring for 1 hour, the oil bath was removed and returned to room temperature, and the transparent NMP solution (henceforth a varnish) of polyamic acid was obtained. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2. Moreover, the test result of the film cured at 350 degreeC is shown in Table 5.

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

In the same manner as in Example 36, the types of diamine 1, tetracarboxylic anhydride 1, tetracarboxylic anhydride 2, and their added mass were changed to those shown in Table 2, respectively, and the same operation as in Example 36 was performed. Got a varnish. In addition, NMP addition amount shown in Table 2 shows the total amount of NMP finally contained in a varnish, and is the mass containing 298 g of NMP which dilutes a silicon-group containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. Moreover, the test result of the film cured at 350 degreeC is shown in Table 5, respectively.

Example 38

Into a 3 L separable flask equipped with a stirring rod equipped with an oil bath, NMP 1200 g was added while introducing nitrogen gas, and 232.4 g of 3,3- (diaminodiphenyl) sulfone (prescribed as diamine 1) was added. After stirring, the mixture was heated to 50 ° C, 40.6 g of terephthalic acid chloride (prescribed as other monomer components) was dissolved in 200 g of γ-butyrolactone, and then added dropwise thereto, followed by stirring for 30 minutes. Subsequently, after 235.4 g of BPDA (prescribed as tetracarboxylic anhydride 1) was added and stirred for 8 hours, both terminal amine-modified methylphenylsilicone oils (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) ( 105.6 g of NMP 298 g was dissolved, and it was added dropwise using a dropping funnel. After heating up at 80 degreeC and stirring for 1 hour, the oil bath was removed and returned to room temperature, and the solution of the transparent polyamic acid was obtained. After 1000 g of NMP was added thereto and diluted, the mixture was added dropwise to 10 L of ion-exchanged water, and the powder of the polyamideimide precursor was precipitated, and the powder was separated by Buchner funnel. This powder was vacuum-dried at 40 degreeC for 48 hours. 1403 g of NMP was added to the powder thus obtained, to obtain an NMP solution of a polyamideimide precursor. The composition here and the weight average molecular weight (Mw) of the obtained polyamide-imide precursor are shown in Table 2. Moreover, the test result of the film cured at 350 degreeC is shown in Table 5.

EXAMPLE 43, 48

In the same manner as in Example 38, the types of diamine 1, tetracarboxylic anhydride 1, and other monomer components, and their added mass were changed to those shown in Table 2, respectively, and the same operation as in Example 38 was performed to obtain a varnish. . In addition, the NMP addition amount shown in Table 2 shows the total amount of NMP finally contained in a varnish. The composition here and the weight average molecular weight (Mw) of the obtained polyamide-imide precursor are shown in Table 2, respectively. Moreover, the test result of the film cured at 350 degreeC is shown in Table 5, respectively.

Example 59

To a 3 L separable flask with a stirring bar equipped with an oil bath, 1000 g of NMP was added while introducing nitrogen gas to 248.30 g of 3,3- (diaminodiphenyl) sulfone (prescribed as diamine 1). It added while stirring, 275.13g of BPDA (it defines with tetracarboxylic anhydride 1) were then added, and it stirred at room temperature for 30 minutes. After heating up this at 50 degreeC and stirring for 12 hours, 104.58 g of both terminal acid anhydride modified methylphenyl silicone oils (made by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (number average molecular weight 4200)) are melt | dissolved in NMP298g, It was added dropwise using a dropping funnel. After heating up at 80 degreeC and stirring for 1 hour, the oil bath was removed and returned to room temperature, and the transparent NMP solution (henceforth a varnish) of polyamic acid was obtained. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 7. Moreover, the test result of the film cured at 350 degreeC is shown in Table 8.

[Examples 60-66]

In the same manner as in Example 59, the diamine 1, the tetracarboxylic anhydride 1, the type of silicon group-containing diamine, and their added mass were changed to those shown in Table 1, respectively, and the same operation as in Example 1 was performed to obtain the varnish. Got it. In addition, the NMP addition amount shown in Table 1 and Table 2 shows the total amount of NMP finally contained in a varnish, and is the mass containing 298 g of NMP which dilutes a silicon-group containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 7, respectively. Moreover, the test result of the film cured at 350 degreeC is shown in Table 8, respectively.

Comparative Example 1

Into a 3 L separable flask equipped with a stirring bar equipped with an oil bath, NMP 1065 g was added while introducing nitrogen gas, and 248.3 g of 3,3- (diaminodiphenyl) sulfone (prescribed as diamine 1) It added while stirring, 218.12g of pyromellitic dianhydrides (it prescribes | regulated as tetracarboxylic anhydride 1) were then added, and it stirred at room temperature for 30 minutes. After heating up this to 50 degreeC and stirring for 12 hours, the oil bath was removed and returned to room temperature, and the transparent NMP solution (henceforth a varnish) of polyamic acid was obtained. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3. Moreover, the test result of the film cured at 350 degreeC is shown in Table 6.

[Comparative Examples 2 to 21]

In the same manner as in Comparative Example 1, the types of diamine 1 and tetracarboxylic anhydride 1 and their added mass were changed to those shown in Table 3, respectively, and the same operation as in Comparative Example 1 was performed to obtain varnishes. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3, respectively. Moreover, the test result of the film cured at 350 degreeC is shown in Table 6, respectively.

Comparative Example 22

Nitrogen gas was introduced into a 3 L separable flask with a stirring rod equipped with an oil bath, 1332 g of NMP was added, 299.8 g of TFMB (defined as diamine 2) was added while stirring, and 294.2 g of BPDA (tetra Carboxylic anhydride 1) was added, and the mixture was heated to 50 ° C and stirred for 12 hours. To this, 105.6 g of both terminal amine-modified methylphenylsilicone oils (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (prescribed as silicon group-containing diamine) was added to a NMP 298 g using a dropping funnel. It dripped. After completion | finish of dripping, this was heated up at 80 degreeC, and after stirring for 1 hour, the oil bath was removed and returned to room temperature, and the slightly cloudy NMP solution of opaque polyamic acid (henceforth a varnish) was obtained. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3. Moreover, the test result of the film cured at 350 degreeC is shown in Table 6.

Example 23

4.36 g (0.02 mol) of pyromellitic anhydride (PMDA) and 25.78 g of BTDA are dispersed in 240 g of N-methyl-2-pyrrolidone (NMP), and ω-ω'-bis- (3-aminopropyl) poly The solution obtained by dissolving 2.4 g of dimethylsiloxane (average molecular weight 480) in 50 g of diethylene glycol dimethyl ether (Dig) was dripped little by little, and it stirred and reacted for 1 hour. Thus, after reacting diaminosiloxane and tetracarboxylic dianhydride, 14.62 g (0.05 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R), and then further 3,3- 11.17 g of DAS was added in small portions.

Example 24

A 1 liter flask with a stirring device, a dropping funnel, a thermometer, a condenser and a nitrogen replacement device was fixed in cold water. 500 g of 3,3'4,4'-benzophenonetetracarboxylic acid 2 of dehydrated and purified N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) after substitution with nitrogen gas in a flask 25.11 g (0.0779 mol) of anhydride (BTDA), 15.48 g (0.0623 mol) of 3,3'-diaminodiphenylsulfone (3,3-DAS) and ω-ω'-bis- (3-aminopropyl) 14.96 g (0.0159 mol) of polydimethylsiloxane (molecular weight 960) was mixed to obtain a polyamic acid solution according to a conventional method.

Example 25

In a 300 ml four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube, 2.87 g (25.1 mmol) of 1,4-diaminocyclohexane and both terminal amino-modified methylphenylsilicon (X22-1660B-) as diamine compounds 3) 3.42 g (0.8 mmol) was added. Subsequently, after nitrogen-substituting the flask, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 8.71 g (25.9 mmol) of diphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (BPDA) was added as a polyhydric carboxylic acid derivative at room temperature, and at that temperature, 24 Stirring was continued for time, and the composition (polyamic acid solution) was obtained.

Example 26

In a 300 ml four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (hereinafter, 7.85 g (24.5 mmol) and 2.03 g (1.6 mmol) of both terminal amino modified methylphenylsilicon (X22-9409) were added. Subsequently, after nitrogen-substituting the flask, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the obtained solution, 5.12 g (26.1 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as "CBDA") as the component (A) was added at room temperature, and in that state. Stirring was continued for 24 hours at the temperature of to obtain a composition (polyamic acid solution).

In addition, the YI value and total light transmittance which are shown to Tables 4-6, 8 show the result (50 ppm / 100 ppm / 500 ppm) when the oxygen concentration in oven is adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively. It is shown.

As shown in Tables 4, 5 and 8, it was confirmed that Examples 1-66 satisfied the following conditions simultaneously in a film physical property.

(1) The residual stress is 25 MPa or less

(2) Yellowness is 7 or less, less influenced by oxygen concentration

(3) The glass transition temperature in the temperature range of room temperature or more is 250 degreeC or more.

(4) The total light transmittance is 88% or more and less influenced by the oxygen concentration.

(5) 30% or more of tensile elongation

(6) NMP chemical resistance test more than 30 minutes

(7) Even if the varnish is manufactured by NMP alone, the total light transmittance is high because the thermosetting film does not become cloudy.

These satisfies the performance for application to a transparent substrate for flexible display of top emission type.

Examples 1-33, 36, 37, 41, 42, 46, 47, 53-66 are 100 nm or less (20-90 nm) of retardation Rth of the film thickness direction derived from birefringence, and are top emission type It satisfies not only the transparent substrate for flexible displays but also the performance for applying to the bottom substrate type flexible display substrate and the touch panel electrode substrate. Moreover, the retardation Rth of the thickness direction is a polyimide which does not use the silicon group containing monomer as a copolymerization monomer (comparative examples 1-22), and the polyimide which uses the silicon group containing monomer (Examples 1-33). In comparison, it can be seen that the polyimide using the silicon group-containing monomer has a smaller Rth, and the silicon group-containing monomer contributes to the Rth reduction of the polyimide.

On the other hand, Comparative Examples 1-26 are low in residual stress, chemical-resistance, and tensile elongation, and YI value and total light transmittance are affected by oxygen concentration at the time of deterioration, and deteriorate.

From these results, the resin obtained from the resin precursor according to the present invention is colorless and transparent, has a low residual stress generated between the inorganic film, excellent chemical resistance, and a YI value due to oxygen concentration at the time of curing. It was confirmed that the resin film had a small influence on the total light transmittance.

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

Industrial availability

The present invention can be suitably used as a substrate, for example, in the manufacture of semiconductor insulating films, TFT-LCD insulating films, electrode protective films, flexible displays, and substrates for touch panel ITO electrodes.

Claims (27)

As a resin precursor obtained by superposing | polymerizing the polymerization component containing an amino group and an amino group reactive group,
The polymerization component comprises a polyvalent compound having two or more groups selected from amino groups and amino group reactive groups,
The polyvalent compound comprises a silicon group-containing compound,
The said polyhydric compound has following formula (1):
[Formula 1]

Containing diamine represented by
The said resin precursor is the following general formula (2):
[Formula 2]

{In formula, two or more R <^3> and R <^4> is a C1-C20 monovalent organic group each independently, and h is an integer of 3-200.}
Has a structure represented by
The amount of the silicon group-containing compound is 6% by mass to 25% by mass based on the total mass of the polyvalent compound.
The resin precursor. The method of claim 1,
A resin precursor comprising at least one of the amino group reactive groups selected from the group consisting of a carboxyl group, a substituted carboxyl group and an acid anhydride group. The method according to claim 1 or 2,
The said silicon group containing compound is the following general formula (3):
[Formula 3]

{In formula, _{two or} more R <_2> is respectively independently a single bond or a C1-C20 divalent organic group, R <_3> and R <_4> is respectively independently a C1-C20 monovalent organic group , R _{5, which} may be present in plural numbers, are each independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ , and L ₃ are each independently an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, It is an acid ester group, an acid halide group, a hydroxyl group, an epoxy group, or a mercapto group, j is an integer of 3-200, k is an integer of 0-197.} The resin precursor containing the silicone compound shown by the following. The method of claim 3, wherein
In General Formula (3), L ₁ and L ₂ are each independently an amino group or an acid anhydride group, and k is 0. The method of claim 4, wherein
Resin precursor in the said General formula (3) whose L <_1> and L <_2> are an amino group together. The method according to any one of claims 1 to 5,
The resin precursor contains unit 1 and unit 2,
The unit 1 is at least the following general formula (4);
[Formula 4]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, X <_{1> which} may exist in multiple numbers each independently represents C4-C20. 32 is a tetravalent organic group, and n is an integer of 1-100.}
The unit 2 has the following general formula (5):
[Formula 5]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, and _{two or} more R <_2> is respectively independently C3-C20 Is a divalent aliphatic hydrocarbon or a divalent aromatic group, R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and a plurality of each of X _{2, which} may be present, are each independently 4 to 4 carbon atoms. 32 is a tetravalent organic group, l is an integer of 3-50, and m is an integer of 1-100.} The structure represented by the following or general formula (6):
[Formula 6]

{In formula, two or more R <_1> is respectively independently a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group, and two or more R <_3> and R <_4> respectively independently represents carbon number R <_{8> which} is a 1-20 monovalent organic group, two or more R <_8> is respectively independently a C3-C20 trivalent aliphatic hydrocarbon or a trivalent aromatic group, p is an integer of 1-100, and q is It is an integer of 3-50.} The resin precursor which has both a structure represented by the general formula (5), or the structure represented by the said General formula (5), and the structure represented by the said General formula (6). The method of claim 6,
The resin precursor whose total amount of the said unit 1 and the said unit 2 is 30 mass% or more on the basis of the total mass of the said resin precursor. The method according to claim 6 or 7,
The said resin precursor is the following general formula (7):
[Formula 7]

{In formula, two or more R <_1> is a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon, or a monovalent aromatic group each independently, X <_{3> which} may exist in multiple numbers each independently represents C4-C20. X _{4 which} may be a 32-valent divalent organic group, and which may exist in multiple numbers each independently is a C4-C32 tetravalent organic group, and t is an integer of 1-100.} The unit 3 which has a structure represented by It further contains a resin precursor. The method of claim 8,
Resin precursor in the said General formula (7) whose X <_3> is the residue which is a structure remove | excluding an amino group from 2,2'-bis (trifluoromethyl) benzidine. The method according to any one of claims 6 to 9,
The unit 1 and the unit 2
A site derived from one or more selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA);
4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid 2 Anhydride (CHDA), 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis (trimelitic acid monoester acid anhydride) (TAHQ), and Sites derived from one or more selected from the group consisting of 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF)
A resin precursor comprising a portion which is a combination thereof in an amount of 60 mol% or more based on the total amount of the acid dianhydride derived portions of the unit 1 and the unit 2. The method according to any one of claims 1 to 10,
Resin precursor which is said R <_3> and said R <_4> respectively independently a C1-C3 monovalent aliphatic hydrocarbon group or a C6-C10 monovalent aromatic hydrocarbon group. The method according to any one of claims 1 to 11,
At least a part of R ₃ and R ₄ is a phenyl group resin precursor. The method according to any one of claims 1 to 12,
Resin obtained by heat-hardening the said resin precursor on condition of 300-500 degreeC in inert atmosphere, the glass transition temperature of at least one of the area | regions of -150 degreeC-0 degreeC, and the glass transition temperature of the area | region of 150 degreeC-380 degreeC And a resin precursor which does not have a glass transition temperature in an area larger than 0 ° C and smaller than 150 ° C. The method according to any one of claims 1 to 13,
The resin precursor containing 20 mol% or more of site | parts derived from biphenyl tetracarboxylic dianhydride (BPDA) based on the total amount of the acid dianhydride-derived site | part of the said resin precursor. The method according to any one of claims 1 to 14,
The resin precursor in which part is imidated. The resin precursor of any one of Claims 1-15, and following General formula (8):
[Formula 8]

{In formula, X <_{3> which} may exist in multiple numbers is respectively independently a C4-C32 tetravalent organic group, and two or more R <_1> represents a hydrogen atom and a C1-C20 monovalent aliphatic hydrocarbon each independently. Or a monovalent aromatic group, and r is an integer of 1 to 100.} A precursor mixture containing a resin precursor having a structure represented by}. The flexible device material containing the resin precursor of any one of Claims 1-15, or the precursor mixture of Claim 16. The resin film which is a hardened | cured material of the resin precursor in any one of Claims 1-15, or a hardened | cured material of the precursor mixture of Claim 16. The resin composition containing the resin precursor of any one of Claims 1-15, or the precursor mixture of Claim 16, and a solvent. The method of claim 19,
After spreading the said resin composition on the surface of a support body, in the 20 micrometer film thickness which resin obtained by imidating the said resin precursor contained in the said resin composition by heating the said resin composition at 300 degreeC-500 degreeC in nitrogen atmosphere, The resin composition whose yellowness is 7 or less. The method of claim 19 or 20,
After developing the said resin composition on the surface of a support body, in the 10 micrometer film thickness which resin obtained by imidating the said resin precursor contained in the said resin composition by heating the said resin composition at 300 degreeC-500 degreeC in nitrogen atmosphere, The resin composition whose residual stress is 25 MPa or less. The resin film which is a hardened | cured material of the resin composition of any one of Claims 19-21. The process of developing the resin composition of any one of Claims 19-21 on the surface of a support body,
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film;
Peeling the resin film from the support
Method for producing a resin film comprising a. The laminated body containing a support body and the resin film which is the hardened | cured material of the resin composition of any one of Claims 19-21 formed on the surface of the said support body. The process of developing the resin composition of any one of Claims 19-21 on the surface of a support body,
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film, thereby obtaining a laminate comprising the support and the resin film.
Method for producing a laminate comprising a. The polyimide resin film whose Rth in 20 micrometers in thickness is 20-90 nm as a polyimide resin film used for manufacture of a display substrate. Developing a resin composition containing a polyimide precursor on the surface of the support;
Heating the support and the resin composition to imidize a polyimide precursor to form a polyimide resin film according to claim 26;
Forming an element on the polyimide resin film;
Process of peeling the said polyimide resin film in which the said element was formed from the said support body
Method of manufacturing a display substrate comprising a.