KR20180048605A - Polyimide precursor, resin composition, and method for producing resin film - Google Patents

Abstract

{식 중, X₁ 은 탄소수 4 ∼ 32 의 4 가의 기를 나타낸다. R₁, R₂, R₃ 은 각각 독립적으로 탄소수 1 ∼ 20 의 1 가의 유기기를 나타낸다. n 은 0 또는 1 을 나타낸다. 그리고 a 와 b 와 c 는 0 ∼ 4 의 정수이다.} 로 나타내는 구조 단위 L 과,
하기 일반식 (2)：

{식 중, X₂ 는 탄소수 4 ∼ 32 의 4 가의 기를 나타낸다.} 로 나타내는 구조 단위 M 을, 1/99 ≤ (구조 단위 L 의 몰수/구조 단위 M 의 몰수) ≤ 99/1 로 포함하는, 폴리이미드 전구체.(a1) a compound represented by the following general formula (1):

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4,
(2): < EMI ID =

(Wherein M represents the number of moles of the structural unit L / m of the structural unit M) < 99/1, wherein the structural unit M represented by the formula ( ₂₎ is a quaternary group having 4 to 32 carbon atoms. Polyimide precursor.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide precursor, a resin composition,

The present invention relates to a method for producing a polyimide precursor, a resin composition and a resin film, for example, used for manufacturing a substrate for a flexible device.

Generally, a film of a polyimide resin is used as a resin film in applications requiring high heat resistance. A general polyimide resin is produced by preparing a polyimide precursor by solution polymerization of an aromatic carboxylic acid dianhydride and an aromatic diamine and then thermally imidizing the polyimide precursor at a high temperature or chemically imidizing it using a catalyst, Resin.

The polyimide resin is an insoluble or refractory super heat resistant resin and has excellent properties such as heat oxidation 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. Examples of applications of the polyimide resin in the field of electronic materials include insulating coatings, insulating films, protective films for semiconductors, electrode protective films for TFT-LCD, and the like. In recent years, adoption as a colorless transparent flexible substrate using lightness and flexibility has been studied instead of a glass substrate conventionally used in the field of display materials.

In the case of producing a polyimide resin film as a flexible substrate, a polyimide resin film is obtained by applying a composition containing a polyimide precursor on a suitable support to form a coating film, followed by heat treatment and imidization. As the support, for example, glass, silicon, silicon nitride, silicon oxide, metal, or the like is used. When a laminate having a polyimide film on such a support is produced, a heat treatment at a high temperature of 250 캜 or more is required for drying and imidization of the polyimide precursor. By this heat treatment, residual stress is generated in the laminate, and serious problems such as warping and peeling occur. This is because the coefficient of linear thermal expansion of the polyimide is larger than that of the material constituting the support.

As the polyimide material having a small thermal expansion coefficient, polyimide formed from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine is most well known. Although it depends on the film thickness and the manufacturing conditions, it has been reported that this polyimide film exhibits a very low coefficient of linear thermal expansion (Non-Patent Document 1).

 It has also been reported that polyimide having an ester structure in the molecular chain exhibits a low linear thermal expansion coefficient because of its appropriate linearity and rigidity (Patent Document 1).

However, a general polyimide resin including the polyimide described in the above document is colored in brown or yellow due to its high directional cyclic density. Therefore, the light transmittance in the visible light region is low, and therefore, Is difficult to use. For example, the polyimide of the non-patent document 1 obtained from 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride and paraphenylenediamine has a yellowness degree (YI Value) is as high as 40 or more, which is insufficient in terms of transparency.

As to the yellowness degree of a film, it is known that polyimide using, for example, a monomer having a fluorine atom exhibits very low yellowing degree (Patent Document 2).

Japanese Patent No. 4627297 Japanese Published Patent Publication No. 2010-538103 Japanese Patent No. 3079867 Specification

 The latest polyimide Japan polyimide study society ENT · S

However, in order to apply the polyimide resin as a colorless transparent flexible substrate, in addition to transparency, excellent physical properties such as elongation and break strength are also required. Particularly recently, along with the TFT device type becoming LTPS (low-temperature polysilicon TFT), a film exhibiting the above properties has been demanded even in the past thermal history.

However, the physical properties of the known transparent polyimide are not sufficient for use as a heat resistant colorless transparent substrate for display.

 Further, the polyimide resin described in Patent Document 1 has a low coefficient of linear thermal expansion, but the polyimide resin film after peeling has a high yellowness index (YI value) as well as high residual stress, The elongation is low and the breaking strength is low.

With regard to the degree of yellowness, the polyimide film described in Patent Document 2 shows a low yellowness in a temperature range of about 300 ° C., but a yellowness (YI value) in a high temperature range of 400 ° C. or more is markedly deteriorated there was.

 Further, polyimide comprising 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ester has been disclosed as a polyimide having a lowered linear expansion coefficient (Patent Document 3).

However, the inventors of the present invention have found that the polyimide resin described in Patent Document 3 has a very thin film for application as a flexible substrate, and there is room for improvement in the degree of yellowing at high temperature.

The present invention has been made in view of the above-described problems. Accordingly, an object of the present invention is to provide a polyimide resin film having low residual stress, low warpage, small yellowing degree (YI value), and high elongation, and a method for producing the same.

The present invention is as follows.

[One]

(a1) a compound represented by the following general formula (1):

[Chemical Formula 1]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4,

(2): < EMI ID =

(2)

Wherein X ₂ represents a tetravalent group having 4 to 32 carbon atoms. And Y is at least one selected from the group consisting of the following general formulas (3), (4) and (5)

1/99? (Number of moles of structural unit L / number of moles of structural unit M)? 99/1

≪ RTI ID = 0.0 > polyimide < / RTI > precursor.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the formulas, R ₄ to R ₁₁ each independently represent a monovalent organic group having 1 to 20 carbon atoms. d ~ k is an integer from 0 to 4.}

[2]

The polyimide precursor according to [1], wherein n in the general formula (1) is 0.

[3]

The polyimide precursor according to [1] or [2], wherein Y in the general formula (2) is a general formula (3).

[4]

The polyimide precursor according to [1] or [2], wherein Y in the general formula (2) is a general formula (4).

[5]

The polyimide precursor according to [1] or [2], wherein Y in the general formula (2) is a general formula (5).

[6]

(a2) a compound represented by the following general formula (10):

[Chemical Formula 6]

And a weight average molecular weight of 30,000 or more and 300,000 or less.

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ). ≪ / RTI > R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

[7]

The polyimide precursor according to [6], wherein the polyimide precursor (a2) has a content of molecules having a weight average molecular weight of less than 1,000 in an amount of less than 5 mass%.

[8]

The polyimide precursor according to [6] or [7], wherein n in the general formula (10) is 0.

[9]

Wherein X ₁ and X ₂ are selected from the group consisting of pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'- The polyimide precursor according to any one of [1] to [5], wherein the polyimide precursor is a tetravalent organic group derived from at least one selected from the group consisting of phenylbis (trimellitic acid monoester acid anhydride) (TAHQ).

[10]

A resin composition comprising the polyimide precursor according to any one of [1] to [9], and (b) an organic solvent.

[11]

The resin composition according to [10], further comprising at least one member selected from the group consisting of (c) a surfactant, and (d) an alkoxysilane compound.

[12]

(11): < EMI ID =

(7)

(Wherein X ₁ and X ₂ represent a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4. Y is at least one member selected from the group consisting of the following general formulas (3), (4) and (5). l and m each independently represent an integer of 1 or more and satisfy the following expression: 0.01? 1 / (1 + m)? 0.99.

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(In the formulas, R ₄ to R ₁₁ each independently represent a monovalent organic group having 1 to 20 carbon atoms. d ~ k is an integer from 0 to 4.}

[13]

(12): < EMI ID =

(11)

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ). ≪ / RTI > R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4, and the elongation is 15% or more.

[14]

A step of forming a coating film by applying a resin composition described in [10] or [11] on the surface of a support,

A step of forming a polyimide resin film by imidizing the polyimide precursor contained in the coating film by heating the support and the coating film;

A step of peeling the polyimide resin film from the support

, Wherein the resin film (2) is formed of a resin.

[15]

The method for producing a resin film according to [14], wherein a step of irradiating a laser beam from the support side is performed prior to the step of peeling the polyimide resin film from the support.

[16]

A step of forming a coating film by applying a resin composition described in [10] or [11] on the surface of a support,

A step of forming a polyimide resin film by imidizing the polyimide precursor contained in the coating film by heating the support and the coating film

Wherein the step of forming the laminate comprises the steps of:

[17]

A step of forming a coating film by applying a resin composition described in [10] or [11] on the surface of a support,

A step of forming a polyimide resin film by imidizing the polyimide precursor contained in the coating film by heating the support and the coating film;

Forming a device or a circuit on the polyimide resin film;

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

Wherein the first and second substrates are bonded to each other.

[18]

(12): < EMI ID =

[Chemical Formula 12]

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ), and R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

The polyimide film for display according to claim 1, wherein the polyimide film is a polyimide film.

[19]

(13): < EMI ID =

[Chemical Formula 13]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4, and a low-temperature polysilicon TFT layer.

[20]

Characterized in that the degree of yellowness at a thickness of 10 microns after heating at 400 DEG C or higher is 20 or less and the absorbance at 308 nm when the film thickness is 1 micron is 0.6 or more and 2.0 or less and the elongation is 15% , Polyimide film.

[21]

(a) a polyimide precursor represented by the following general formula (1)

(b) an organic solvent,

(c) a surfactant, and (d) an alkoxysilane compound.

Wherein the resin composition further comprises a resin.

[Chemical Formula 14]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

The polyimide film obtained from the polyimide precursor and the resin composition according to the present invention has low residual stress, low warpage, small yellowishness (YI value), and high elongation.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a structure of an organic EL substrate manufactured in Examples and Comparative Examples; Fig.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, exemplary embodiments of the present invention (hereinafter referred to as " embodiments ") will be described in detail. Further, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention. Unless otherwise specified, the characteristic values described in this disclosure are intended to be values measured by the method described in the section of [Examples], or equivalents thereof, by methods understood by those skilled in the art.

<Resin composition>

An embodiment of the present invention provides a resin composition comprising (a) a polyimide precursor and (b) an organic solvent.

Hereinafter, each component will be described in turn.

[Polyimide precursor]

The polyimide precursor as the first embodiment of the present invention,

(a1) a compound represented by the following general formula (1):

[Chemical Formula 15]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4,

(2): &lt; EMI ID =

[Chemical Formula 16]

Wherein X ₂ represents a tetravalent group having 4 to 32 carbon atoms. Y is at least one selected from the group consisting of the following general formulas (3), (4) and (5)

1/99? (Number of moles of the structural unit L / number of moles of the structural unit M)? 99/1.

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

(In the formulas, R ₄ to R ₁₁ each independently represent a monovalent organic group having 1 to 20 carbon atoms. d ~ k is an integer from 0 to 4.}

The polyimide precursor of the first embodiment of the present invention has low residual stress, low warpage, small yellowishness (YI value), and high elongation when made into a polyimide film. In addition, the polyimide precursor of the first embodiment of the present invention has a low yellowness value (YI value) in a high temperature region when it is a polyimide film.

Here, R ₁ to R ₃ are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of such an organic group include alkyl groups such as methyl group, ethyl group and propyl group, halogen-containing groups such as trifluoromethyl group, and alkoxy groups such as methoxy group and ethoxy group. Among them, the methyl group is preferable from the viewpoint of YI in the high temperature region.

Here, a, b, c, and d are not limited as long as they are an integer of 0 to 4. Of these, an integer of 0 to 2 is preferable from the standpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.

Here, n is 0 or 1. Of these, 0 is preferable from the viewpoint of YI in the high temperature region.

The lower limit of the molar ratio of the structural unit L to the structural unit M (the number of moles of the structural unit L / m of the structural unit M) may be 5/95, 10/90, 20/80 or 30/70 Or 40/60. The upper limit of the molar ratio of the structural unit L to the structural unit M (the number of moles of the structural unit L / the number of moles of the structural unit M) may be 95/5, 90/10, 80/20 or 70/30, 60/40.

X ₁ and X ₂ are each independently a tetravalent group having 4 to 32 carbon atoms and may be the same or different. Tetravalent organic groups derived from the following tetracarboxylic acid dianhydrides are exemplified.

Specific examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides having 8 to 36 carbon atoms, aliphatic tetracarboxylic acid dianhydrides having 6 to 36 carbon atoms, and alicyclic tetracarboxylic dianhydrides having 6 to 36 carbon atoms And a tetracarboxylic acid dianhydride. Among them, an aromatic tetracarboxylic acid dianhydride having a carbon number of 8 to 36 is preferable from the viewpoint of the yellowness in a high temperature region. Here, the carbon number includes the number of carbons contained in the carboxyl group.

More specifically, examples of the aromatic tetracarboxylic acid dianhydride having 8 to 36 carbon atoms include 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- 3-methyl-cyclohexene-1,2-dicarboxylic acid anhydride, pyromellitic acid dianhydride (hereinafter, also referred to as PMDA), 1,2,4-dioxotetrahydro- Benzene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter also referred to as BPDA), 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2- Lidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene- Dicarboxylic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (Hereinafter also referred to as TAHQ) thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride (hereinafter also referred to as ODPA), p-phenylenebis (trimellitic acid anhydride) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxy Benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, , 2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4- , 4-dicarboxyphenoxy) dimethylsilyl Bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1, , 4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2, 3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, and the like.

Examples of the aliphatic tetracarboxylic acid dianhydride having 6 to 50 carbon atoms include ethylene tetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride and the like;

As the alicyclic tetracarboxylic acid dianhydride having 6 to 36 carbon atoms, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexane-1, Tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride (hereinafter referred to as CHDA), 3,3 ', 4,4'-bis Cyclohexanetetracarboxylic acid dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane- Dicarboxylic acid dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis 1,2-dicarboxylic acid dianhydride, 2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy- (Cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, Bis (cyclohexane -1,2-dicarboxylic acid dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel- [1S, 5R, 6R] -3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'- -Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis- (3,4-dicarboxylic anhydride phenyl ) Ether, and the like.

From the viewpoint of CTE, chemical resistance, balance of Tg and yellowness in the high temperature range, PMDA, BPDA, TAHQ and ODPA are preferable, and BPDA and TAHQ are more preferable.

The polyimide precursor in the embodiment may be a polyamideimide precursor by using a dicarboxylic acid in addition to the above-described tetracarboxylic acid dianhydride to the extent that the performance thereof is not impaired. By using such a precursor, various performances such as improvement in mechanical elongation, improvement in glass transition temperature, and reduction in yellowness can be adjusted in the obtained film. As such a dicarboxylic acid, there can be mentioned a dicarboxylic acid having an aromatic ring and an alicyclic dicarboxylic acid. Particularly an aromatic dicarboxylic acid having 8 to 36 carbon atoms and an alicyclic dicarboxylic acid having 6 to 34 carbon atoms. Here, the carbon number includes the number of carbons contained in the carboxyl group.

Of these, dicarboxylic acids having an aromatic ring are preferable.

Specific examples thereof include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 3-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulfonyl bisbenzoic acid, 3, 4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'- 9,4-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9, 9'-diphenyldicarboxylic acid, 2,2'- 4,4'-bis (4-carboxyphenoxy) biphenyl, 4,4'-bis (4-carboxyphenoxy) 3,4'-bis (4-carboxyphenoxy) biphenyl, 3,4'-bis Bis (3-carboxyphenoxy) biphenyl, 4,4'-bis (4-carboxyphenoxy) biphenyl, 3,3'- (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) 4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,3'-bis (4-carboxyphenoxy) -m -Terphenyl, 3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3-carboxyphenoxy) -m-terphenyl, 3-carboxyphenoxy) -p-terphenyl, 3,3'-bis , 3'-bis (3-carboxyphenoxy) -m-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2- , 4,4'-benzophenone dicarboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid and the like; and

And 5-aminoisophthalic acid derivatives described in International Publication WO 2005/068535 pamphlet. When these dicarboxylic acids are actually copolymerized with the polymer, they may be used in the form of an acid chloride derivative or an active ester derivative derived from thionyl chloride or the like.

The weight average molecular weight (Mw) of the polyimide precursor in the present embodiment is preferably 10,000 to 300,000, particularly preferably 30,000 to 200,000. If the weight average molecular weight is more than 10,000, mechanical characteristics such as elongation and breaking strength are excellent, residual stress is low, and YI is low. When the weight average molecular weight is less than 300,000, the weight average molecular weight can be easily controlled at the time of the synthesis of the polyamic acid, and a resin composition having an appropriate viscosity can be obtained, and the applicability of the resin composition is improved. In the present disclosure, the weight average molecular weight is a value obtained as a standard polystyrene conversion value using gel permeation chromatography (hereinafter also referred to as GPC).

In the polyimide precursor of the present embodiment, the content of molecules having a molecular weight of less than 1,000 is preferably less than 5 mass%, more preferably less than 1 mass%, based on the total amount of the polyimide precursor. The polyimide film formed from the resin composition obtained by using such a polyimide precursor is low in residual stress and is preferable from the viewpoint that the haze of the inorganic film formed on the polyimide film becomes low.

The content of the molecule having a molecular weight of less than 1,000 with respect to the total amount of the polyimide precursor can be calculated from the peak area obtained by conducting GPC measurement using a solution in which the polyimide precursor is dissolved.

As the diamine used in the structural unit represented by the general formula (1) in the present embodiment, a diamine represented by the following general formula (6) can be exemplified.

[Chemical Formula 20]

(Wherein R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms, n represents 0 or 1, and a, b and c are integers of 0 to 4)

Examples of R ₁ and R ₂ include alkyl groups such as methyl group, ethyl group and propyl group, halogen-containing groups such as trifluoromethyl group, and alkoxy groups such as methoxy group and ethoxy group. Among them, the methyl group is preferable from the viewpoint of YI in the high temperature region.

Here, a and b are not limited provided that they are an integer of 0 to 4. Of these, an integer of 0 to 2 is preferable from the standpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.

More specifically, when n is 0, 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate -Aminobenzoate (4,3-APAB), and the like.

When n is 1, [4- (4-aminobenzoyl) oxyphenyl] 4-aminobenzoate and the like can be exemplified.

As the diamine used in the structural unit represented by the general formula (3) in the present embodiment, a diamine represented by the following general formula (7) can be mentioned.

[Chemical Formula 21]

(Wherein R ₄ and R ₅ each independently represent a monovalent organic group having 1 to 20 carbon atoms, and d and e are integers of 0 to 4.)

Here, R ₄ and R ₅ are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of such an organic group include alkyl groups such as methyl group, ethyl group and propyl group, halogen-containing groups such as trifluoromethyl group, and alkoxy groups such as methoxy group and ethoxy group. Among them, the methyl group is preferable from the viewpoint of YI in the high temperature region.

Here, c and d are not limited as long as they are an integer of 0 to 4. Of these, an integer of 0 to 2 is preferable from the standpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.

More specifically, 4,4'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone can be exemplified.

As the diamine used in the structural unit represented by the general formula (4) in the present embodiment, a diamine represented by the following general formula (8) can be exemplified.

[Chemical Formula 22]

Here, R ₆ and R ₇ are each independently not limited to a monovalent organic group having 1 to 20 carbon atoms. Examples of such an organic group include alkyl groups such as methyl group, ethyl group and propyl group, halogen-containing groups such as trifluoromethyl group, and alkoxy groups such as methoxy group and ethoxy group. Among them, the methyl group is preferable from the viewpoint of YI in the high temperature region.

Each of R ₈ and R ₉ independently represents a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom. Examples of the organic group include an alkyl group such as a methyl group, an ethyl group and a propyl group, a halogen-containing group such as a trifluoromethyl group, and an alkoxy group such as a methoxy group and an ethoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

f, g, h, and i are each independently not limited as long as an integer of 0 to 4. Of these, an integer of 0 to 2 is preferable from the standpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.

Z is a single bond, a methylene group, an ethylene group, an ether, a ketone, or the like. Of these, single bonds are more preferable from the viewpoint of YI in the high temperature region.

More specifically, it is possible to use 9,9-bis (aminophenyl) fluorene, 9,9-bis (4-amino- Fluorene, 9,9-bis (4-hydroxy-3-aminophenyl) fluorene, and 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene. It is preferable to use at least one selected.

As the diamine used in the structural unit represented by the general formula (5) in the present embodiment, a diamine represented by the following general formula (9) can be mentioned.

(23)

Here, R ₁₀ and R ₁₁ are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of such an organic group include alkyl groups such as methyl group, ethyl group and propyl group, halogen-containing groups such as trifluoromethyl group, and alkoxy groups such as methoxy group and ethoxy group. Among them, the methyl group is preferable from the viewpoint of YI in the high temperature region.

Each of j and k is not limited as long as it is independently an integer of 0 to 4. Of these, an integer of 0 to 2 is preferable from the standpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.

More specifically, 2,2'-bis (trifluoromethyl) benzidine and the like can be mentioned.

The polyimide film formed from the polyimide precursor of the first embodiment of the present invention has low residual stress, low warpage, low yellowing degree (YI value) at high temperature region, and high elongation.

As a second embodiment of the present invention,

(a2) a compound represented by the following general formula (10):

&Lt; EMI ID =

And a polyimide precursor having a weight average molecular weight of 30,000 or more and 300,000 or less can be provided.

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ). &Lt; / RTI &gt; R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

Here, X ₃ is not limited as long as it is a tetravalent organic group derived from at least one selected from ODPA, BPDA and TAHQ, but BPDA and TAHQ are preferable from the viewpoint of CTE and Tg.

Here, R ₁ to R ₃ are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of such an organic group include alkyl groups such as methyl group, ethyl group and propyl group, halogen-containing groups such as trifluoromethyl group, and alkoxy groups such as methoxy group and ethoxy group. Among them, the methyl group is preferable from the viewpoint of YI in the high temperature region.

Here, a, b, c, and d are not limited as long as they are an integer of 0 to 4. Of these, an integer of 0 to 2 is preferable from the standpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.

Here, n is 0 or 1. Of these, 0 is preferable from the viewpoint of YI in the high temperature region.

As the diamine for the structure represented by the general formula (10), a diamine used in the general formula (6) can be used.

The weight average molecular weight (Mw) of the polyimide precursor in the second embodiment is 30,000 to 300,000. When the weight average molecular weight is more than 30,000, mechanical characteristics such as elongation and breaking strength are excellent, residual stress is low, and YI is low. When the weight average molecular weight is less than 300,000, the weight average molecular weight can be easily controlled at the time of the synthesis of the polyamic acid, and a resin composition having an appropriate viscosity can be obtained, and the applicability of the resin composition is improved. Among these, the weight average molecular weight (Mw) is more preferably from 35000 to 250000, and particularly preferably from 40000 to 2300000.

In the polyimide precursor of the second embodiment, the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass, and more preferably less than 1% by mass based on the total amount of the polyimide precursor. The polyimide film formed from the resin composition obtained by using such a polyimide precursor is low in residual stress and is preferable from the viewpoint that the haze of the inorganic film formed on the polyimide film becomes low.

The content of the molecule having a molecular weight of less than 1,000 with respect to the total amount of the polyimide precursor can be calculated from the peak area obtained by conducting GPC measurement using a solution in which the polyimide precursor is dissolved.

The polyimide precursor of the second embodiment is excellent in storage stability and excellent in coatability. The polyimide film formed from the polyimide precursor of the second embodiment of the present invention has low residual stress, low warpage, low yellowing (YI value), high elongation, and high breaking strength.

The polyimide precursor in the first and second embodiments may contain, in addition to the diamines represented by the above-mentioned general formulas (6) to (9), other polyimide precursors in addition to the diamine Diamines may be used.

Examples of other diamines include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3 ' Diaminodiphenylsulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, (Aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4,4- ] Ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3- Aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2 Bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- Fluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, and the like, and it is preferable to use at least one selected from these.

The content of the other diamine in the total diamine is preferably 20 mol% or less, and particularly preferably 10 mol% or less.

[Production of polyimide precursor]

The polyimide precursor (polyamic acid) of the present invention is obtained by reacting a tetracarboxylic acid dianhydride with a diamine (for example, APAB) used in the structural unit represented by the above-mentioned general formula (1) (For example, 4,4'-DAS) used in a structural unit represented by the general formula (1) below. This reaction is preferably carried out in a suitable solvent. Concretely, for example, there is a method of dissolving a predetermined amount of APAB and 4,4'-DAS in a solvent, adding a predetermined amount of tetracarboxylic acid dianhydride to the obtained diamine solution and stirring .

In the diamine component, the molar ratio of the diamine used in the structural unit represented by the general formula (1) to the diamine used in the structural unit represented by the general formula (2) is not limited to 99/1 to 1/99. When the diamine used in the structural unit represented by the general formula (2) is at least 1 mol%, the yellowness tends to be good, and the diamine used in the structural unit represented by the general formula (1) is at least 1 mol% , The warp after the formation of the inorganic film on the obtained polyimide film tends to be good. The molar ratio of the diamine used in the structural unit represented by the formula (1) to the diamine used in the structural unit represented by the formula (2) is preferably 95/5 to 50/50, more preferably 90/10 to 50/50 More preferable. The molar ratio of the diamine used in the structural unit represented by the general formula (1) and the diamine used in the structural unit represented by the general formula (2) may be 80/20 to 50/50, or 70/30 to 50/50 do. The molar ratio of the diamine used in the structural unit represented by the general formula (1) is preferably not less than the molar ratio of the diamine used in the structural unit represented by the general formula (2).

The polyimide precursor of the second embodiment can be obtained by reacting a tetracarboxylic acid dianhydride (for example, TAHQ) with a diamine (for example, APAB) used in the structural unit represented by the aforementioned general formula (6) , And a polycondensation reaction can be carried out. This reaction is preferably carried out in a suitable solvent. Specifically, for example, a method of dissolving a predetermined amount of APAB in a solvent, adding a predetermined amount of TAHQ to the obtained diamine solution, and stirring.

The ratio (molar ratio) of the tetracarboxylic acid dianhydride component to the diamine component at the time of synthesizing the polyimide precursor is determined by the thermal expansion coefficient, residual stress, elongation, and yellowness (hereinafter also referred to as YI) Is preferably in the range of tetracarboxylic acid dianhydride: diamine = 100: 90 to 100: 110 (0.90 to 1.10 molar parts of diamine relative to 1 molar part of tetracarboxylic acid dianhydride) , And 100: 95 to 100: 105 (0.95 to 1.05 molar parts of diamine relative to 1 molar part of the acid dianhydride).

In the present embodiment, when synthesizing a polyamic acid which is a preferred polyimide precursor, the molecular weight is adjusted by adjusting the ratio of the tetracarboxylic acid dianhydride component to the diamine component and by adding a terminal sealing agent It is possible to control. The closer the ratio of the acid anhydride component to the diamine component is at 1: 1, and the smaller the amount of the end sealant used, the larger the molecular weight of the polyamic acid.

It is recommended that a high-purity product be used as the tetracarboxylic acid dianhydride component and the diamine component. The purity is preferably 98% by mass or more, more preferably 99% by mass or more, and further preferably 99.5% by mass or more. When a plurality of kinds of acid anhydride or diamine components are used in combination, it is sufficient that the acid anhydride component or the diamine component as a whole has the above-mentioned purity. However, the total of the acid anhydride component and the diamine component, Of the purity.

The solvent of the reaction is not particularly limited as long as it is a solvent capable of dissolving a tetracarboxylic acid dianhydride component, a diamine component, and a resulting polyamic acid, and a polymer having a high molecular weight. Specific examples of such solvents include, for example, aprotic solvents, phenol solvents, ether solvents and glycol solvents. As specific examples of these,

Examples of the aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) Lactam, 1,3-dimethylimidazolidinone, tetramethylurea, the following general formula (13):

(25)

Amide solvents such as echamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) represented by R ₁₂ = methyl group and echamide B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) represented by R ₁₂ = n-butyl group;

lactone solvents such as? -butyrolactone and? -valerolactone;

Aminic based solvents such as hexamethylphosphoric amide and hexamethylphosphinutriamide;

A sulfur-based solvent such as dimethylsulfone, dimethylsulfoxide and sulfolane;

Ketone solvents such as cyclohexanone and methylcyclohexanone;

Tertiary amine type solvents such as picoline and pyridine;

Acetic acid (2-methoxy-1-methylethyl)

My back:

Examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5- 6-xylenol, 3,4-xylenol, 3,5-xylenol, and the like:

Examples of the ether and glycol solvents include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) 2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane and the like,

Respectively.

The boiling point of the solvent used in the synthesis of the polyamic acid at normal pressure is preferably 60 to 300 占 폚, more preferably 140 to 280 占 폚, and particularly preferably 170 to 270 占 폚. If the boiling point of the solvent is higher than 300 占 폚, the drying step becomes necessary for a long time. On the other hand, if the boiling point of the solvent is lower than 60 캜, roughness on the surface of the resin film, mixing of bubbles into the resin film, and the like may occur during the drying process, and a uniform film may not be obtained.

Thus, it is preferable to use a solvent having a boiling point of 170 to 270 DEG C, more preferably a vapor pressure of 250 Pa or less at 20 DEG C from the viewpoints of solubility and edge catoration upon coating. More specifically, it is preferable to use at least one member selected from the group consisting of N-methyl-2-pyrrolidone,? -Butyrolactone, and the compound represented by the formula (11).

The water content in the solvent is preferably 3,000 ppm by mass or less.

These solvents may be used alone or in combination of two or more.

The polyimide precursor (a) in this embodiment preferably has a content of molecules having a molecular weight of less than 1,000 in an amount of less than 5% by mass.

It is considered that the presence of a molecule having a molecular weight of less than 1,000 in the polyimide precursor (a) is considered to be due to the fact that the water content of the solvent used in synthesis is involved. That is, it is considered that some of the acid anhydride groups of the acid dianhydride monomer is hydrolyzed by moisture to become a carboxyl group, and remains in a state of low molecular weight without high molecular weight. Therefore, the water content of the solvent used in the polymerization reaction should be as small as possible. The water content of the solvent is preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less.

The water content of the solvent varies depending on the grade of the solvent used (dehydrated grade, universal grade, etc.), the solvent container (bottle, 18 L can, canister cans, etc.) Time (use immediately after opening, use after lapse of time after opening, etc.), and the like. It is also considered that the substitution of the rare gas in the reactor prior to the synthesis, the presence or absence of the rare gas flow during the synthesis, and the like are also involved. Therefore, in the synthesis of the polyimide precursor (a), it is necessary to use a high-purity product as a raw material, use a solvent having a low water content, and take measures to prevent moisture from entering the system before and during the reaction It is recommended.

When each monomer component is dissolved in a solvent, it may be heated if necessary.

The reaction temperature for the synthesis of the polyimide precursor (a) is preferably 0 to 120 캜, more preferably 40 to 100 캜, and still more preferably 60 to 100 캜. By performing the polymerization reaction at this temperature, a polyimide precursor having a high polymerization degree can be obtained. The polymerization time is preferably 1 to 100 hours, more preferably 2 to 10 hours. When the polymerization time is 1 hour or more, a polyimide precursor having a uniform polymerization degree is obtained. When the polymerization time is 100 hours or less, a polyimide precursor having a high degree of polymerization can be obtained.

In a preferred embodiment of the present embodiment, the (a1) polyimide precursor and the (a2) polyimide precursor have the following characteristics.

(a) a solution obtained by dissolving a polyimide precursor in a solvent (for example, N-methyl-2-pyrrolidone) is applied to the surface of a support, and then the solution is heated under a nitrogen atmosphere (For example, 1 hour) at 300 to 550 占 폚 (for example, 430 占 폚), the yellow color of the resin obtained by imidizing the polyimide precursor 30 or less.

(a) a solution obtained by dissolving a polyimide precursor in a solvent (for example, N-methyl-2-pyrrolidone) is applied to the surface of a support, and then the solution is heated under a nitrogen atmosphere (For example, 1 hour) at 300 to 550 占 폚 (for example, 430 占 폚), the residual stress is 25 MPa or less in a resin obtained by imidizing the polyimide precursor.

The polyimide precursor according to the present embodiment may contain, if necessary, a polyimide precursor represented by the following general formula (14):

(26)

(In the general formula (14), plural R &lt; ₁₃ &gt; s are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group,

X ₄ is a tetravalent organic group having 4 to 32 carbon atoms,

Y is a divalent organic group having 4 to 32 carbon atoms. only,

(Excluding the structural units corresponding to the general formula (1) and the general formula (6) above) may be further contained in the polyimide precursor.

In the general formula (14), R ₁₃ is preferably a hydrogen atom. X ₃ is preferably a tetravalent aromatic group from the viewpoint of heat resistance, reduction of YI value, and total light transmittance. Y is preferably a divalent aromatic group or an alicyclic group from the viewpoints of heat resistance, reduction of YI value, and total light transmittance.

The mass ratio of the polyimide precursor having the structural unit represented by the general formula (14) in the polyimide precursor (a) according to the present embodiment is preferably 80% by mass or less based on the total amount of the polyimide precursor (a) By mass and not more than 70% by mass is more preferable from the viewpoint of reduction of oxygen dependency of YI value and total light transmittance.

In a preferred embodiment of the present embodiment, the polyimide precursor (a1) and the polyimide precursor (a2) may be partially imidized. In this case, the imidization ratio is preferably 80% or less, and more preferably 50% or less. This partial imidization is obtained by heating the polyimide precursor (a) and dehydrating and pulverizing it. This heating is preferably carried out at a temperature of 120 to 200 DEG C, more preferably 150 to 180 DEG C, preferably 15 to 20 hours, and more preferably 30 to 10 hours.

 Further, N, N-dimethylformamide dimethylacetal or N, N-dimethylformamide diethyl acetal is added to the polyamic acid obtained by the above-mentioned reaction and heated, and a part or all of the carboxylic acid is esterified Then, by using the polyimide precursor (a) in this embodiment as a polyimide precursor, a resin composition having improved viscosity stability at room temperature can be obtained. These ester-modified polyamic acids can be obtained by additionally reacting the above-mentioned acid anhydride component with a dehydrating condensation agent such as monohydric alcohol equivalent to one equivalent of an acid anhydride group and thionyl chloride or dicyclohexylcarbodiimide Followed by condensation reaction with the diamine component.

The proportion of (a) the polyimide precursor (preferably polyamic acid) in the resin composition of the present embodiment is preferably from 3 to 50 mass%, more preferably from 5 to 40 mass% , And particularly preferably from 10 to 30 mass%.

<Resin composition>

Another aspect of the present invention provides a resin composition containing the above-mentioned (a) polyimide precursor and (b) an organic solvent. This resin composition is typically a varnish.

[(b) Organic solvent]

The organic solvent (b) in the present embodiment is not particularly limited as long as it can dissolve the polyimide precursor (a) and other optional components used arbitrarily. As the organic solvent (b), the solvent described above as (a) a solvent usable in the synthesis of the polyimide precursor may be used. Preferred organic solvents are also the same as above. The organic solvent (b) in the resin composition of the present embodiment may be the same as or different from the solvent used for the synthesis of the polyimide precursor (a).

The amount of the organic solvent (b) is preferably such that the solid content of the resin composition is 3 to 50% by mass. It is also preferable that the viscosity of the resin composition (25 ° C) is 500 mPa · s to 100,000 mPa · s, and (b) after the composition and amount of the organic solvent are adjusted.

[Other ingredients]

The resin composition of the present embodiment may further contain (c) a surfactant, (d) an alkoxysilane compound and the like in addition to the components (a) and (b).

The resin composition related to this embodiment includes at least one member selected from the group consisting of (a) a polyimide precursor, (b) an organic solvent, (c) a surfactant, and (d) an alkoxysilane compound.

The skeleton of the polyimide precursor is not limited to the skeleton described above in the first and second aspects. That is, the skeleton of the polyimide precursor is not particularly limited as long as it is a skeleton represented by the following general formula (1).

(27)

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

((c) Surfactant)

By adding a surfactant to the resin composition of the present embodiment, the applicability of the resin composition can be improved. Specifically, occurrence of streaks in the coating film can be prevented.

Such surfactants include, for example, silicone surfactants, fluorochemical surfactants, and nonionic surfactants other than these surfactants. In these examples,

Examples of the silicone surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092 and X-70-093 (trade names, manufactured by Shin-Etsu Chemical Co., SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (trade names, manufactured by Toray Dow Corning Silicone Co.), SILWET L-77, L-7001 and FZ- DBE-824, DBE-621, CMS-626, CMS-222 (trade names, KF-352A, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378 and BYK- (Manufactured by Japan Chemical Industry Co., Ltd.), glanol (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.);

Examples of the fluorine surfactant include Megapac F171, F173, R-08 (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated), Fluorad FC4430 and FC4432 (trade name, Sumitomo 3M;

Examples of the nonionic surfactant other than these surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.

Among these surfactants, a silicone surfactant and a fluorinated surfactant are preferable from the viewpoint of coating properties (streak suppression) of the resin composition. From the viewpoint of the influence on the YI value and the total light transmittance by the oxygen concentration in the curing process, Surfactants are preferred.

When the surfactant (c) is used, the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the polyimide precursor (a) in the resin composition.

(d) an alkoxysilane compound

In order to make the resin film obtained from the resin composition according to the present embodiment exhibit sufficient adhesion with the support in a manufacturing process of a flexible device or the like, the resin composition preferably contains (a) a polyimide precursor , And 0.01 to 20% by mass of an alkoxysilane compound. When the content of the alkoxysilane compound relative to 100 mass% of the polyimide precursor is 0.01 mass% or more, good adhesion with the support can be obtained. The content of the alkoxysilane compound is preferably 20 mass% or less from the viewpoint of the storage stability of the resin composition. The content of the alkoxysilane compound is more preferably 0.02 to 15 mass%, further preferably 0.05 to 10 mass%, particularly preferably 0.1 to 8 mass%, based on 100 mass parts of the polyimide precursor.

By using the alkoxysilane compound as the additive of the resin composition according to the present embodiment, in addition to the above-described improvement in the adhesion property, the coating property of the resin composition (suppression of stripe unevenness) is improved, The concentration dependency can be lowered.

Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, gamma -Aminopropyltrimethoxysilane,? -Aminopropyltripropoxysilane,? -Aminopropyltributoxysilane,? -Aminoethyltriethoxysilane,? -Aminoethyltripropoxysilane,? -Aminoethyltribe Aminobutyltrimethoxysilane,? -Aminobutyltrimethoxysilane,? -Aminobutyltrimethoxysilane,? -Aminobutyltrimethoxysilane,? -Aminobutyltriethoxysilane,? -Aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, (P-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol and alkoxysilane compounds , And one kind selected from these Phase is preferably used.

(28)

The method for producing the resin composition in the present embodiment is not particularly limited. For example, the following method can be used.

When the solvent used for synthesizing the polyimide precursor (a) and the organic solvent (b) are the same, the polyimide precursor solution thus synthesized can be directly used as the resin composition. If necessary, at least one of (b) an organic solvent and other components may be added to the polyimide precursor in a temperature range of room temperature (25 ° C) to 80 ° C, followed by stirring and mixing, and then . For this stirring mixing, a suitable device such as a three-one motor (with a stirring blade) (manufactured by Shinto Chemical Co., Ltd.), a revolving mixer or the like can be used. If necessary, heat of 40 to 100 ° C may be applied.

On the other hand, when the solvent used in the synthesis of the polyimide precursor (a) and the organic solvent (b) are different, the solvent in the synthesized polyimide precursor solution is appropriately subjected to, for example, (A) after isolating the polyimide precursor, (b) adding an organic solvent and, if necessary, other components in a temperature range of from room temperature to 80 ° C, and stirring and mixing.

After the resin composition is prepared as described above, the composition solution is heated at, for example, 130 to 200 ° C for 5 minutes to 2 hours, for example, so that a part of the polyimide precursor is dehydrated to the extent that the polymer does not precipitate You can even make it. Here, the imidization rate can be controlled by controlling the heating temperature and the heating time. By partially imidizing the polyimide precursor, the viscosity stability of the resin composition at room temperature can be improved. The imidization rate is preferably 5% to 70% from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition solution and the storage stability of the solution.

It is preferable that the resin composition according to the present embodiment has a water content of 3,000 mass ppm or less.

The water content of the resin composition is more preferably 1,000 mass ppm or less, and still more preferably 500 mass ppm or less, from the viewpoint of viscosity stability when the resin composition is stored.

The solution viscosity of the resin composition according to the present embodiment is preferably 500 to 200,000 mPa 占 퐏 at 25 占 폚, more preferably 2,000 to 100,000 mPa 占 퐏, and particularly preferably 3,000 to 30,000 mPa 占 퐏. This solution viscosity can be measured using an E-type viscometer (VISCONICEHD, manufactured by TOKI INDUSTRIAL CO., LTD.). When the solution viscosity is lower than 300 mPa s, it is difficult to apply at the time of film formation, and when it is higher than 200,000 mPa 문제, there is a possibility that the stirring at the time of synthesis becomes difficult.

(a) When the polyimide precursor is synthesized, even if the solution has a high viscosity, after the completion of the reaction, a solvent is added and stirred to obtain a resin composition of good handleability.

The resin composition of this embodiment has the following characteristics in a preferred embodiment.

The resin composition is applied to the surface of the support to form a coating film and then the coating film is heated in a nitrogen atmosphere (for example, nitrogen having an oxygen concentration of 2,000 ppm or less) at 300 ° C to 550 ° C, In the resin film obtained by imidizing the polyimide precursor has a yellowness index YI of 30 or less at a film thickness of 10 mu m.

The resin composition is applied to the surface of the support to form a coating film and then the coating film is heated in a nitrogen atmosphere (for example, nitrogen having an oxygen concentration of 2,000 ppm or less) at 300 ° C to 550 ° C, , The residual stress is 25 MPa or less. In the resin film obtained by imidizing the polyimide precursor, the residual stress is 25 MPa or less.

The resin composition according to the present embodiment can be suitably used for forming a transparent substrate of a display device such as, for example, a liquid crystal display, an organic electroluminescence display, a field emission display, or an electronic paper. Specifically, it can be used for forming a substrate of a thin film transistor (TFT), a substrate of a color filter, a substrate of a transparent conductive film (ITO, Indium Tin Oxide) or the like.

The resin precursor of the present embodiment can easily form a polyimide film having a residual stress of 25 MPa or less and thus can be easily applied to a display manufacturing process provided with a TFT element device on a colorless transparent polyimide substrate.

&Lt; Resin film &

Another aspect of the present invention provides a resin film formed from the resin precursor described above.

Still another aspect of the present invention provides a method for producing a resin film from the resin composition described above.

In the resin film in this embodiment,

A step (coating step) of forming a coating film by applying the above-mentioned resin composition on the surface of a support,

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

A step of peeling the polyimide resin film from the support (peeling step)

And a control unit.

Here, the support is not particularly limited as long as it has heat resistance at a heating temperature in subsequent steps and has good releasability. For example, glass (e.g., alkali-free glass) substrates;

Silicon wafers;

(Ethylene terephthalate), poly (ethylene terephthalate), OPP (stretched polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide, polyetheretherketone, A resin substrate such as a sulphone or polyphenylene sulfide;

Metal substrates such as stainless steel, alumina, copper, and nickel

Etc. are used.

In the case of forming a film-like polyimide molding, for example, a glass substrate, a silicon wafer, or the like is preferable. In the case of forming a film or sheet-like polyimide molding, for example, PET (polyethylene Terephthalate), OPP (stretched polypropylene), and the like.

Examples of the application method include a coating method such as a doctor blade knife coater, an air knife coater, a roll coater, a rotary coater, a flow coater, a die coater, a bar coater, etc., a spin coating method, a spray coating method and a dip coating method; A printing technique typified by screen printing and gravure printing, and the like can be applied.

The coating thickness should be appropriately adjusted depending on the thickness of the desired resin film and the content of the polyimide precursor in the resin composition, but is preferably about 1 to 1,000 占 퐉. The application step is sufficient at room temperature, but may be carried out by heating the resin composition at a temperature in the range of 40 to 80 ° C for the purpose of lowering the viscosity and improving workability.

The coating step may be followed by a drying step. Alternatively, the drying step may be omitted and the subsequent heating step may be carried out directly. This drying step is carried out for the purpose of removing the organic solvent. When the drying process is carried out, suitable devices such as, for example, a hot plate, a box-type dryer, a conveyor-type dryer and the like can be used. The drying step is preferably carried out at 80 to 200 캜, more preferably at 100 to 150 캜. The operating time of the drying step is preferably from 1 minute to 10 hours, more preferably from 3 minutes to 1 hour.

As described above, a coating film containing a polyimide precursor is formed on a support.

Subsequently, a heating step is carried out. The heating step is a step of removing the organic solvent remaining in the coating film in the above drying step and advancing the imidization reaction of the polyimide precursor in the coating film to obtain a film made of polyimide.

This heating step can be carried out using an apparatus such as an inert gas oven, a hot plate, a box-type dryer, a conveyor-type dryer, or the like. This step may be carried out simultaneously with the above-mentioned drying step, or both steps may be carried out sequentially.

The heating step may be carried out in an air atmosphere, but it is recommended that the heating step be carried out in an inert gas atmosphere from the viewpoints of safety, transparency of the obtained polyimide film, and YI value. Examples of the inert gas include nitrogen and argon.

The heating temperature may be appropriately set depending on the kind of the organic solvent (b), but is preferably 250 ° C to 550 ° C, more preferably 300 to 450 ° C. If the temperature is 250 占 폚 or higher, imidization becomes sufficient, and if it is 550 占 폚 or lower, there is no problem such as deterioration of transparency and deterioration of heat resistance of the obtained polyimide film. The heating time is preferably about 0.5 to 3 hours.

In the present embodiment, the oxygen concentration in the ambient atmosphere in the heating step is preferably 2,000 mass ppm or less, more preferably 100 mass ppm or less, and more preferably 10 mass% or less, in view of the transparency and YI value of the polyimide film to be obtained. ppm or less. By heating in an atmosphere having an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be made 30 or less.

Depending on the intended use and purpose of the polyimide resin film, a peeling step for peeling the resin film from the support after the above heating step is required. This peeling step is preferably carried out after the resin film on the support is cooled to about room temperature to 50 캜.

As the peeling step, for example, the following embodiments (1) to (4) can be mentioned.

(1) After the structure including the polyimide resin film / support is produced by the above method, the interface between the support and the polyimide resin film is subjected to ablation processing by irradiating a laser from the support side of the structure, . Examples of the laser include a solid (YAG) laser, a gas (UV excimer) laser, and the like. It is preferable to use a spectrum having a wavelength of 308 nm or the like (see Japanese Unexamined Patent Publication No. 2007-512568 and Japanese Unexamined Patent Publication No. 2012-511173).

(2) A method for forming a release layer on a support before coating a resin composition on a support, and then obtaining a constitution including a polyimide resin film / release layer / support and peeling off the polyimide resin film. Examples of the release layer include a method using parylene (registered trademark, manufactured by Nippon Parylene Co., Ltd.), a method using tungsten oxide, and a method using a release agent such as a vegetable oil system, a silicone system, a fluorine system, and an alkyd system. (See Japanese Laid-Open Patent Publication Nos. 2010-67957 and 2013-179306).

The method (2) and the laser irradiation of the above (1) may be used in combination.

(3) A method for obtaining a polyimide resin film by obtaining a constitution including a polyimide resin film / support by using a metal substrate which can be etched as a support, and then etching the metal with an etchant. As the metal, for example, copper (specifically, an electrolytic copper foil "DFF" manufactured by Mitsui Mining and Mining Co., Ltd.), aluminum and the like can be used. As the etchant, ferric chloride or the like may be used for copper, and dilute hydrochloric acid may be used for aluminum.

(4) After obtaining a constitution including the polyimide resin film / support by the above method, an adhesive film is attached to the surface of the polyimide resin film to separate the pressure-sensitive adhesive film / polyimide resin film from the support, And separating the polyimide resin film from the backing adhesive film.

Among these peeling methods, the method (1) or (2) is suitable from the viewpoints of the difference in refractive index, YI value and elongation of the obtained polyimide resin film from the front and rear sides of the obtained polyimide resin film, Method (1) is more appropriate.

When copper is used as the support in the method (3), the YI value of the obtained polyimide resin film tends to be larger and the degree of elongation tends to decrease. This is thought to be the effect of copper ions.

The thickness of the resin film obtained by the above method is not particularly limited, but is preferably in the range of 1 to 200 占 퐉, more preferably 5 to 100 占 퐉.

The resin film according to the present embodiment may have a yellowness index YI of 30 or less at a film thickness of 10 mu m. The residual stress may be 25 MPa or less. In particular, the yellowness YI at a film thickness of 10 mu m is 30 or less and the residual stress may be 25 MPa or less. Such characteristics can be obtained, for example, by mixing the resin precursor of the present disclosure in a nitrogen atmosphere (for example, in an oxygen concentration of 2,000 ppm or less), preferably 300 ° C to 550 ° C, more preferably 350 ° C to 450 ° C Lt; RTI ID = 0.0 &gt; C, &lt; / RTI &gt;

The resin film according to the present embodiment may further have a tensile elongation of 15% or more. The tensile elongation of the resin film may be 20% or more, particularly 30% or more. The tensile elongation can be measured using a commercially available tensile tester using a resin film having a film thickness of 10 mu m as a sample.

The resin film according to the present embodiment is a film made of polyimide in which the (a1) polyimide precursor contained in the above-mentioned resin composition is thermally imidized. Therefore, the following general formula (11):

[Chemical Formula 29]

(Wherein X ₁ and X ₂ represent a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4. Y is at least one member selected from the group consisting of the general formulas (3), (4) and (5). l and m each independently represent an integer of 1 or more, and have a structural unit represented by 0.01? 1 / (1 + m)? 0.99.

The lower limit of l / (l + m) may be 0.05, 0.10, 0.20, 0.30, or 0.40.

The upper limit of l / (l + m) may be 0.95, 0.90, 0.80, 0.70, or 0.60.

As described above, preferably, the residual stress is 25 MPa or less, YI is 30 or less, the glass transition temperature is 400 占 폚 or more, the elongation is 15% or more, and the breaking strength is 250 MPa or more.

The second embodiment is a film made of polyimide in which the polyimide precursor (a2) contained in the above-mentioned resin composition is thermally imidized. Therefore, the following general formula (12):

(30)

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ). &Lt; / RTI &gt; R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are an integer of 0 to 4, and the elongation is 15% or more. Preferably, the resin film has a residual stress of 25 MPa or less, YI of 30 or less, A glass transition temperature of 400 DEG C or more, and a breaking strength of 250 MPa or more.

<Laminate>

Another aspect of the present invention provides a laminate comprising a support and a polyimide resin film formed from the resin composition on the surface of the support.

Still another aspect of the present invention provides a method for producing the laminate.

In the laminate of the present embodiment,

A step (coating step) of forming a coating film on the surface of a support by applying the above-mentioned resin composition,

And a step of heating the support and the coating film to imidize the polyimide precursor contained in the coating film to form a polyimide resin film (heating step).

The production method of the laminate may be carried out in the same manner as the production method of the resin film described above except that the peeling step is not performed, for example.

The laminate can be suitably used, for example, in the production of a flexible device.

More specifically, it is as follows.

In the case of forming a flexible display, a glass substrate is used as a support, a flexible substrate is formed thereon, and a TFT or the like is formed thereon. The step of forming a TFT or the like on a flexible substrate is typically performed at a temperature in a wide range of 150 to 650 占 폚. However, in order to realize a desired performance in practice, a TFT-IGZO (InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si-TFT ). &Lt; / RTI &gt;

On the other hand, these properties of the polyimide film tend to lower various physical properties (in particular, yellowness and elongation) due to these thermal hysteresis, and when it exceeds 400 ° C, the yellowness and elongation are particularly lowered. However, the polyimide film obtained from the polyimide precursor according to the present invention has a very low yellowing degree and elongation at a high temperature of 400 DEG C or higher, and can be preferably used in this region.

Further, in the present embodiment, a laminate including a polyimide film layer containing a polyimide represented by the following general formula (13) and an LTPS (low-temperature polysilicon TFT) layer can be provided.

(31)

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

As a production method of the laminate, an amorphous Si layer is formed after the laminate including the above-mentioned support and a polyimide resin film formed from the above-mentioned resin composition on the surface of the support, Deg.] C for 0.5 to 3 hours, and then crystallized by an excimer laser or the like to form an LTPS layer. Thereafter, the glass and the polyimide film are peeled off by laser ablation or the like to obtain the laminate.

A laminate including a polyimide film layer containing a polyimide represented by the general formula (13) and a LTPS (low temperature polysilicon TFT) layer is less likely to peel or swell after a heat cycle test and has less substrate warpage.

Further, when the residual stress generated in the flexible substrate and the polyimide resin film is high, when the stacked body made of both expand in the high temperature TFT process and then shrink upon cooling at room temperature, the glass substrate is warped and broken, Problems such as peeling from the glass substrate may occur. Generally, since the thermal expansion coefficient of the glass substrate is smaller than that of the resin, residual stress is generated between the glass substrate and the flexible substrate. As described above, the resin film according to the present embodiment can be suitably used for forming a flexible display because the residual stress generated between the resin film and the glass substrate can be 25 MPa or less.

In addition, the polyimide film according to the present embodiment can have a yellowness degree YI of 30 or less at a film thickness of 10 mu m and a tensile elongation of 15% or more. Thus, the resin film according to the present embodiment is excellent in breaking strength when the flexible substrate is handled, and therefore, the yield when the flexible display is manufactured can be improved.

As another aspect, it is preferable that the degree of yellowness at a thickness of 10 microns after heating at 400 DEG C or higher is 20 or less, the absorbance at 308 nm when the film thickness is 0.1 micron is 0.6 or more and 2.0 or less, and the elongation is 15 % Or more of a polyimide film.

By setting the YI to 20 or less, a flexible substrate can be manufactured without deteriorating the image quality in the display.

More preferably 18 or less, and particularly preferably 16 or less.

The absorbance at 308 nm when the film thickness is 0.1 micron is 0.6 or more and 2.0 or less, and the elongation is 15% or more. Thus, for example, the polyimide film can be easily peeled from the glass substrate with the laser. From the viewpoint of suppressing the ash after delamination of the laser, it is preferable that the elongation is not less than 0.6 and not more than 1.5 and the elongation is not less than 20%. For example, from the viewpoint of not lowering the performance of the organic EL device, Particularly preferred.

The upper limit of the elongation is not particularly limited but may be 80% or less, 70% or less, 60% or less, 50% or less, or 40% or less.

 In addition, there is a case where the polyimide film is burned with the laser light at the time of delamination of the laser, and the residue is ashes.

Accordingly, another aspect of the present invention provides a display substrate.

Still another aspect of the present invention provides a method of manufacturing the display substrate.

In the display substrate manufacturing method of this embodiment,

A step (coating step) of forming a coating film by applying the above-mentioned resin composition on the surface of a support,

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

A step of forming an element or a circuit on the polyimide resin film (element / circuit forming step)

A step of peeling the polyimide resin film on which the element or circuit is formed from the support (peeling step)

And a control unit.

In the above method, the application step, the heating step and the peeling step can be carried out in the same manner as the above-mentioned method for producing a resin film.

The element / circuit forming process can be carried out by a method known to a person skilled in the art.

The resin film according to the present embodiment satisfying the above physical properties is suitably used for applications in which use of the conventional polyimide film is restricted by the yellow color, particularly for a colorless transparent substrate for a flexible display, a protective film for a color filter, and the like. (For example, an interlayer of a TFT-LCD, a gate insulating film, a liquid crystal alignment film, etc.), an ITO substrate for a touch panel, a cover glass for a smartphone, etc. It can be used also in a field where colorless transparency and low birefringence are required such as a resin substrate. Application of the polyimide according to the present embodiment as a liquid crystal alignment film makes it possible to manufacture a TFT-LCD having a high aperture ratio and a high contrast ratio.

The resin film and the laminate produced using the polyimide precursor and the resin precursor according to the present embodiment can be applied to, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, It can be suitably used as a substrate in particular. Examples of the flexible device to which the resin film and the laminate according to the present embodiment can be applied include a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, a flexible lighting, and a flexible battery.

Example

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

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

&Lt; Measurement of weight average molecular weight &gt;

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) under the following conditions.

As a solvent, 24.8 mmol / l of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 m &lt; 2 &gt; (Manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatograph) was added and dissolved. The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Toso Co., Ltd.).

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

Flow rate: 1.0 ml / min

Column temperature: 40 DEG C

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: ultraviolet visible light absorber, manufactured by JASCO)

&Lt; Evaluation of content of molecules having a molecular weight of less than 1,000 (content of a low molecular weight material)

The content of the molecules having a molecular weight of less than 1,000 in the resin was calculated as the ratio (percentage) of the peak area occupied by the component having a molecular weight of less than 1,000 to the peak area of the entire molecular weight distribution, using the measurement result of GPC obtained above.

<Evaluation of Water Content>

The water content of the synthetic solvent and the resin composition (varnish) was measured using a Karl Fischer moisture measuring apparatus (a very small moisture measuring apparatus AQ-300, manufactured by Hiranuma Industrial Co., Ltd.).

&Lt; Evaluation of viscosity stability of resin composition &gt;

With respect to the resin compositions prepared in each of Examples and Comparative Examples,

After the preparation, the sample after standing for 3 days at room temperature was subjected to viscosity measurement at 23 ° C as a sample after preparation;

Thereafter, the sample which was allowed to stand at room temperature for 2 weeks was used as a sample after 2 weeks, and the viscosity was measured again at 23 占 폚. These viscosities were measured using a viscometer (TV-22 manufactured by Toki Industry Co., Ltd.) equipped with a warm-up period.

Using the measured values, the rate of change in viscosity at room temperature for 2 weeks was calculated by the following equation.

(Viscosity of sample after preparation) - (viscosity of sample after preparation)] / (viscosity of sample after preparation) x 100

The viscosity change rate at room temperature for 2 weeks was evaluated by the following criteria.

⊚: viscosity change rate is 5% or less (storage stability "excellent")

?: Viscosity change rate exceeding 5% and 10% or less (storage stability "good")

X: Viscosity change rate exceeded 10% (storage stability "poor")

<Evaluation of varnish application property>

The resin composition prepared in each of Examples and Comparative Examples was coated on a non-alkali glass substrate (size 37 mm x 47 mm, thickness 0.7 mm) using a bar coater so as to have a thickness of 15 mu m after curing, And pre-baked for 60 minutes.

The application of the varnish was evaluated by measuring the level difference of the surface of the coating film by using a stepped system (manufactured by Tencor Corporation, type name P-15).

?: The step difference of the surface is not more than 0.1 占 퐉 (coating property "good")

?: The difference in level of the surface was more than 0.1 and 0.5 占 퐉 or less (coatability "good")

X: The step difference of the surface exceeds 0.5 占 퐉 (coating property is "poor")

<Evaluation of Residual Stress>

Each resin composition was coated on a 6-inch silicon wafer having a thickness of 625 占 퐉 占 25 占 퐉, which had been previously measured for "bending amount", by a spin coater and prebaked at 100 占 폚 for 7 minutes. Thereafter, the oxygen concentration in the warehouse was adjusted to 10 mass ppm or less using a vertical curing furnace (model name VF-2000B, manufactured by Koyo Lindberg), and heating at 430 占 폚 for 1 hour A curing treatment (curing treatment) was carried out to prepare a silicon wafer having a polyimide resin film with a thickness of 10 mu m after curing.

The amount of deflection of the wafer was measured using a residual stress measuring apparatus (model name FLX-2320, manufactured by Tencor Corporation), and the residual stress generated between the silicon wafer and the resin film was evaluated.

⊚: residual stress of -5 seconds 15 MPa or less (evaluation of residual stress "excellent")

?: Residual stress exceeding 15 but not exceeding 25 MPa (evaluation of residual stress "good")

X: residual stress exceeding 25 MPa (evaluation of residual stress &quot; defective &quot;)

&Lt; Evaluation of bending of polyimide resin film having inorganic film &

The resin compositions prepared in each of Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate having an aluminum vapor deposition layer formed thereon so as to have a film thickness of 10 占 퐉 after curing and prebaked at 100 占 폚 for 7 minutes. Thereafter, the oxygen concentration in the warehouse was adjusted to 10 mass ppm or less by using a bell-shaped cure (model name VF-2000B, manufactured by Koyo Lindberg), and heat curing treatment was conducted at 430 캜 for 1 hour, To thereby prepare a wafer having a mid resin film. Using this wafer, a silicon nitride (SiNx) film as an inorganic film was formed to a thickness of 100 nm at 350 DEG C on a polyimide resin film by a CVD method, and a laminated wafer having an inorganic film / polyimide resin formed thereon .

The laminate wafer obtained above was immersed in a dilute hydrochloric acid aqueous solution, and the two layers of the inorganic film and the polyimide film were integrally formed and peeled from the wafer to obtain a sample of a polyimide film having an inorganic film formed on its surface. Using this sample, the warpage of the polyimide resin film was evaluated.

&Amp; cir &amp;: No warping (warp &quot; good &quot;)

&Amp; cir &amp;: A piece having no warpage (warp &quot; good &quot;)

X: The film is rounded due to warping (deflection &quot; defective &quot;)

&Lt; Evaluation of yellowness (YI value) &gt;

A wafer (one having no inorganic film) was produced in the same manner as in &lt; evaluation of bending of the polyimide resin film having an inorganic film formed thereon. The wafer was immersed in a dilute hydrochloric acid aqueous solution and the polyimide resin film was peeled off to obtain a resin film.

The obtained polyimide resin film was measured for YI value (in terms of a film thickness of 10 mu m) using a D65 light source with a Spectrophotometer (SE600) manufactured by Nippon Denshoku Industries Co.,

&Lt; Evaluation of elongation and fracture strength &gt;

A wafer (one having no inorganic film) was produced in the same manner as in &lt; evaluation of bending of the polyimide resin film having an inorganic film formed thereon. Using a dicing saw (DAD 3350, manufactured by Disco Co., Ltd.), a nick of 3 mm in width was inserted into the polyimide resin film of the wafer, the resin film piece was immersed in the dilute hydrochloric acid aqueous solution and dried. This sample was cut into a length of 50 mm.

The elongation and fracture strength of the above samples were measured at a test speed of 40 mm / min and an initial weight of 0.5 fs using TENSILON (UTM-II-20 manufactured by Orientech).

&Lt; Measurement of absorbance of polyimide resin film at 308 nm &gt;

Each of the varnishes was spin-coated on a quartz glass substrate and heated at 430 占 폚 for 1 hour in a nitrogen atmosphere to obtain a polyimide resin film having a thickness of 0.1 占 퐉. For these polyimide membranes, the absorbance at 308 nm was measured using UV-1600 (Shimadzu Corporation).

[Example 1]

96 g of N-methyl-2-pyrrolidone (NMP) was added to a nitrogen-substituted 500 ml separable flask, and 17.71 g (77.6 mmol) of 4-aminophenyl-4-aminobenzoate (APAB) , 4'-diaminodiphenylsulfone (DAS) (4.82 g, 19.4 mmol) were placed and stirred to dissolve APAB and DAS. Thereafter, 29.42 g (100 mmol) of biphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride (BPDA) was added and the polymerization reaction was carried out under nitrogen flow at 80 ° C for 3 hours with stirring Respectively. Thereafter, the solution was cooled to room temperature, and NMP was added to adjust the solution viscosity to 51,000 mPa.s to obtain an NMP solution of polyamic acid (hereinafter, also referred to as varnish) P-1. The polyamic acid thus obtained had a weight average molecular weight (Mw) of 65,000.

[Examples 2 to 21 and Comparative Examples 1 to 5]

In the same manner as in Example 1 except that the amount of the raw material (molar ratio), the kind of the solvent used, the polymerization temperature, and the polymerization time were changed as described in Table 1, the varnish P- 2 to P-26.

The weight average molecular weight (Mw) of the polyamic acid contained in each varnish is shown in Table 1.

The abbreviations of the respective components in Table 1 have the following meanings.

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

PMDA: pyromellitic acid dianhydride

TAHQ: p-phenylenebis (trimellitic acid anhydride)

APAB: 4-aminophenyl-4-aminobenzoate

ATAB: 2-methyl-4-aminophenyl-4-aminobenzoate

BABB: [4- (4-aminobenzoyl) oxyphenyl] 4-aminobenzoate

BAFL: 9,9-bis (aminophenyl) fluorene

BFAF: 9,9-bis (4-amino-3-fluorophenyl) fluorene

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

DAS: 4,4'-diaminodiphenyl sulfone

NMP: N-methyl-2-pyrrolidone

DMF: N, N-dimethylformamide

DMAc: N, N-dimethylacetamide

The varnishes P-1 to P-26 obtained in the above Examples and Comparative Examples were directly used as a resin composition, and evaluated according to the above-described method. The evaluation results are shown in Table 2.

As is evident from Tables 1 and 2, the polyimide films obtained in Comparative Examples 1 and 2 containing only the structural units represented by the general formula (1) could not evaluate the physical properties such as elongation of the films. Also, the residual stress was high. In addition, the polyimide film obtained in Comparative Example 3 containing only the structural unit represented by the general formula (2) had a high residual stress and was warped after forming the inorganic film, and the elongation was also low.

On the other hand, the polyimide films obtained from Examples 1 to 21, which contain the structural units represented by the general formula (1) and the structural units represented by the general formula (2) in a molar ratio of 99/1 to 1/99, Of 20 or less, residual stress of 25 MPa or less, and elongation of 20% or more. In addition, even when the warp occurred after the formation of the inorganic film did not occur, or even when it occurred, the warp was extremely insignificant.

From the results shown in Table 2, it was confirmed that the polyimide resin film obtained from the resin composition according to the present invention was a resin film having a low yellowing degree, low residual stress, and excellent mechanical properties.

Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness index YI of 30 or less, and an elongation of 15% or more is obtained.

[Example 22]

N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm) immediately after the opening of the 18 L can was added to a nitrogen-substituted 500 mL separable flask in an amount corresponding to the solid content of 17 wt% 5.71 g (25.0 mmol) of aminophenyl-4-aminobenzoate (APAB, purity: 99.5%, manufactured by Nihon Junyu Yakuhin KK) was added and stirred to dissolve APAB. Thereafter, 7.36 g (25.0 mmol) of biphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride (BPDA, purity 99.5%, manufactured by Manak Co.) was added, Under stirring for 3 hours. Thereafter, the solution was cooled to room temperature, and NMP was added to adjust the solution viscosity to 51,000 mPa.s to obtain an NMP solution of polyamic acid (hereinafter also referred to as varnish) P-27. The weight average molecular weight (Mw) of the obtained polyamic acid was 128,000, and the content of molecules having a molecular weight of less than 1,000 was 0.01 mass%.

[Examples 23 to 33 and Comparative Examples 6 to 11]

In the same manner as in Synthesis Example 1, except that the kind of the starting material, the amount of the raw material, the kind of the solvent used, the polymerization temperature and the polymerization time were changed as described in Table 3, the varnish P -28 to P-44.

The weight average molecular weights (Mw) of the polyamic acid contained in each varnish are shown together in Table 3.

The abbreviations of the respective components in Table 3 have the following meanings.

BPDA: biphenyltetracarboxylic acid dianhydride, purity 99.5%, manufactured by Mitsubishi Chemical Corporation

TAHQ: p-phenylenebis (trimellitic acid anhydride), purity 99.5%, manufactured by Manak Co., Ltd.

PMDA: pyromellitic acid dianhydride

APAB: 4-aminophenyl-4-aminobenzoate, purity 99.5%

4,3-APAB: 4-aminophenyl-3-aminobenzoate, purity 99.5%

ATAB: 2-methyl-4-aminophenyl-4-aminobenzoate

BABB: [4- (4-aminobenzoyl) oxyphenyl] 4-aminobenzoate

NMP 1:18 l After the opening of the can, moisture content 250 ppm

NMP 2: 500 ml bottles, left standing for 1 month after opening, moisture content 3,070 ppm

DMF: 500 ml bottled, after opening, moisture content 3510 ppm

DMAc: 500 ml bottles, after opening, moisture content 3430 ppm

[Examples 22 to 33 and Comparative Examples 6 to 11]

The varnishes P-27 to P-44 obtained in the above Examples and Comparative Examples were directly used as a resin composition, and evaluated in accordance with the above-described method. The evaluation results are shown in Table 4.

As is clear from Table 3 and Table 4, Comparative Example 6 (P-39), Comparative Example 7 (P-40), and Comparative Example 8 (P-41) in which the polyimide precursor (varnish) ), Comparative Example 10 (P-43) and Comparative Example 11 (P-44) had large residual stress and large warpage. In addition, the degree of yellowness was large, and elongation and breaking strength were small. Particularly, in Comparative Examples 10 and 11 in which the water content was large, the film was very stiff.

On the other hand, in Comparative Example 9 (P-42) in which the weight average molecular weight of the polyimide precursor was 30,000 or more, the residual stress and warpage were small, the yellowness was low, the elongation and fracture strength were great, .

In contrast, in Examples 22 to 33 using polyimide precursors P-27 to P-38 having a weight average molecular weight of 30,000 or more and 300,000 or less, the residual stress was low, the warpage was low, the yellowness was low, Excellent breaking strength was obtained, and excellent results were obtained in any of the characteristics.

From the results shown in Table 4, it was confirmed that the polyimide resin film obtained from the resin composition according to the present invention is a resin film having low yellowing degree, low residual stress, and excellent mechanical properties.

Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness degree YI of 20 or less, a glass transition temperature of 400 ° C or more, an elongation of 15% or more and a breaking strength of 250 MPa or more .

In the following Examples 34 to 45, the effects of adding at least one kind selected from the group consisting of a surfactant and an alkoxysilane compound to the resin composition were tested.

[Example 34]

First, the varnish P-27 obtained in Example 22 was used as the resin composition as it was, and coating stripes were evaluated by the following procedure.

&Lt; Evaluation of coating stripes (coating property) &gt;

The above resin composition was coated on a non-alkali glass substrate (size 37 mm x 47 mm, thickness 0.7 mm) using a bar coater so as to have a thickness of 15 mu m after curing. After coating, it was allowed to stand at room temperature for 10 minutes, and it was visually confirmed whether coating stripes were formed on the obtained coating film. Three coatings were carried out using the same resin composition, and the number of coating stripes was examined for each coating film, and the average value was evaluated according to the following criteria.

⊚: No coating continuous stripes having a width of 1 mm or more and a length of 1 mm or more (evaluation of coating stripes "excellent")

&Amp; cir &amp;: One or two coating stripes (evaluation of coating stripes &quot; good &

?: 3 to 5 coating stripes (evaluation of coating stripes "good")

The evaluation results are shown in Table 5.

[Examples 35 to 45]

A surfactant or alkoxysilane compound of the kind and amount shown in Table 5 was added as an additional additive to the varnish P-27 obtained in Example 22, and then filtered with a filter of 0.1 占 퐉 to prepare a resin composition.

Using the resin composition, evaluation of the coating stripes was carried out in the same manner as in Example 34. [ The results are shown in Table 5.

The abbreviations of the respective components in Table 5 are as follows. The amount of these components used in Table 5 is the blending amount (amount used) with respect to 100 parts by weight of the polyimide precursor contained in the varnish. In Examples 39 and 45, Surfactant 1 and alkoxysilane compound 1 were used in combination.

Surfactant 1: DBE-821, product name, silicone surfactant, manufactured by Gelest

Surfactant 2: Megafac F171, product name, fluorochemical surfactant, DIC manufacture

Alkoxysilane compound 1: Compound represented by the following formula (AS-1)

Alkoxysilane Compound 2: Compound represented by the following formula (AS-2)

(32)

As is apparent from Table 5, in Examples 35 to 39 containing the surfactant or alkoxysilane compound and in Examples 41 to 45, the occurrence of the coating stripe was suppressed as compared with Examples 34 and 40 which contained no surfactant or alkoxysilane compound, A polyimide resin film excellent in surface smoothness was obtained.

[Example 46]

The varnish P-27 was coated on a non-alkali glass substrate (size 37 mm x 47 mm, thickness 0.7 mm) using a bar coater so as to have a thickness of 10 mu m after curing and then prebaked at 140 DEG C for 60 minutes. Subsequently, the mixture was adjusted to have an oxygen concentration of 10 mass ppm or less in a warehouse using a vertical cure (model name VF-2000B, manufactured by Koyo Lindberg Co.), and subjected to a heat curing treatment at 430 캜 for 1 hour, A glass substrate having a resin film formed thereon was produced. An amorphous silicon layer was formed on the polyimide film, dehydrogenation annealing was performed at 430 占 폚 for 1 hour, and then an excimer laser was irradiated to form an LTPS layer. The glass substrate was peeled off by an excimer laser (wavelength: 308 nm, repetition frequency: 300 Hz) to obtain a laminate including a polyimide film and an LTPS layer.

This laminate had no warpage and had a yellow degree of 20 or less.

[Example 47]

A laminate was obtained in the same manner as in Example 46 except that the varnish P-1 was used. This laminate had no warpage and had a yellow degree of 20 or less.

[Comparative Example 12]

A laminate was obtained in the same manner as in Example 46 except that varnish P-24 was used. This laminate had a large warpage, and a crack occurred in a part of the polyimide film.

[Synthesis Example]

2.24 g (9.8 mmol) of APAB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean-Stark apparatus and a reflux condenser under nitrogen atmosphere, and the APAB was dissolved under stirring. Then, 2.24 g (10.0 mmol) of H-PMDA was added thereto, refluxed at 180 占 폚 for 2 hours, and toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask was cooled to 40 ℃, 1,650 ㎝ derived from an amide bond from the IR ^- it was confirmed that the absorption of near ¹ (C = O) is lost. Thereafter, 8.95 g (39.2 mmol) of APAB, 121.6 g of NMP, 6.54 g (30.0 mmol) of PMDA and 4.44 g (10.0 mmol) of 6FDA were added and stirred at 80 ° C for 4 hours to obtain a polyimide -Polyamic acid polymer varnish was obtained (P-45). The polyimide-polyamic acid polymer thus obtained had a weight average molecular weight (Mw) of 82,000.

[Examples 48 to 53 and Comparative Example 13]

An organic EL substrate as shown in Fig. 1 was produced.

A polyimide precursor varnish (P-1, P-11, P-20, P-22, P-27, P-33 and P- After curing, the coating was applied so as to have a film thickness of 10 mu m and then pre-baked at 140 DEG C for 60 minutes. Subsequently, the mixture was adjusted to have an oxygen concentration of 10 mass ppm or less in a warehouse using a vertical cure (model name VF-2000B, manufactured by Koyo Lindberg Co.), and subjected to a heat curing treatment at 430 캜 for 1 hour, A glass substrate having a resin film formed thereon was produced.

Subsequently, a SiN layer was formed to a thickness of 100 nm by a CVD (Chemical Vapor Deposition) method.

Subsequently, titanium was deposited by a sputtering method and then patterned by a photolithography method to form a scanning signal line.

Next, a SiN layer was formed to a thickness of 100 nm on the entire glass substrate on which the scanning signal lines were formed by the CVD method. (Up to now is referred to as the lower substrate 2a)

Subsequently, an amorphous silicon layer 256 was formed on the lower substrate 2a, dehydrogenation annealing was performed at 430 占 폚 for 1 hour, and then an excimer laser was irradiated to form an LTPS layer.

Thereafter, the entire surface of the lower substrate 2a is coated with a photosensitive acrylic resin by a spin coating method, and exposed and developed by a photolithography method to form an interlayer insulating film 258 having a plurality of contact holes 257 . A part of each LTPS 256 is exposed by the contact hole 257.

Next, an ITO film is formed on the entire surface of the lower substrate 2a on which the interlayer insulating film 258 is formed by the sputtering method, and exposed and developed by the photolithography method, and patterning is performed by the etching method. A lower electrode 259 is formed so as to form a pair.

 Further, in each contact hole 257, the lower electrode 252 penetrating the interlayer insulating film 258 and the LTPS 256 are electrically connected.

Next, after the barrier ribs 251 are formed, the hole transport layer 253 and the light emitting layer 254 are formed in the spaces partitioned by the barrier ribs 251. The upper electrode 255 was formed so as to cover the light emitting layer 254 and the barrier ribs 251. The organic EL substrate 25 was produced by the above process.

Next, a UV curable resin was coated on the periphery of the glass substrate, the polyimide film of this embodiment and the sealing substrate 2b formed in this order, and the sealing substrate 2b and the organic EL substrate were placed in an argon gas atmosphere Thereby bonding the organic EL device. Thus, a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.

An excimer laser (wavelength 308 nm, repetition frequency 300 Hz) was irradiated from the side of the lower substrate 2a and the side of the encapsulation substrate 2b of the laminate thus formed and peeled off with the minimum energy necessary for peeling the entire surface Respectively.

The laminate was evaluated for substrate warpage, lighting test, and cloudiness evaluation of the laminate after peeling. Heat cycle tests were also conducted. The results are shown in Table 6.

&Lt; Substrate warpage &

◎: Without warping

○: There is little warping

[Delta]: Rounded by bending

<Lighting test>

○: Lighted

X: Not lit

&Lt; Evaluation of laminate white count &gt;

After the formation of the layered product, the whole device was transparent, &amp; cir &amp;

<Heat Cycle Test>

Appearance observation was carried out after 1000 cycles of testing at -5 占 폚 and 60 占 폚 for 30 minutes (transfer time of tank (tank) 1 minute) using an Espec production heat cycle tester.

?, No peeling or swelling was observed?, No peeling or swelling after the test was observed?, And peeling or swelling after peeling was observed.

[Examples 54 to 58, Comparative Example 14]

A polyimide precursor varnish (P-1, P-11, P-20, P-22, P-27, P-33 and P-45) was used and LTPS was changed to IGZO Otherwise, the laminate was produced, and the above test was carried out. The results are shown in Table 7.

[Examples 59 to 63 and Comparative Example 15]

(P-1, P-11, P-20, P) having an absorbance of 308 nm at a YI of 20 or less and a film thickness of 0.1 microns of 0.6 or more and 2.0 or less and an elongation of at least 15% (Ash) when irradiated with energy of 10 mJ / cm &lt; 2 &gt; added to the minimum energy and the minimum energy necessary for delamination of the laser at the time of peeling the laser, )) Were evaluated. A case where no ash was generated at all, a case where a little ash was observed at the edge, The results are shown in Table 8.

The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the invention.

Industrial availability

The resin film formed from the polyimide precursor of the present invention can be applied to, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protecting film, etc., a flexible display, a substrate for a touch panel ITO electrode, It can be suitably used as a substrate.

Claims (21)

(a1) a compound represented by the following general formula (1):
[Chemical Formula 1]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4,
(2): &lt; EMI ID =
(2)

Wherein X ₂ represents a tetravalent group having 4 to 32 carbon atoms. Y is at least one member selected from the group consisting of the following general formulas (3), (4) and (5)
1/99? (Number of moles of the structural unit L / number of moles of the structural unit M)? 99/1.
(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the formulas, R ₄ to R ₁₁ each independently represent a monovalent organic group having 1 to 20 carbon atoms. d ~ k is an integer from 0 to 4.} The method according to claim 1,
Wherein n in the general formula (1) is 0 is a polyimide precursor. 3. The method according to claim 1 or 2,
A polyimide precursor wherein Y in the general formula (2) is a general formula (3). 3. The method according to claim 1 or 2,
The polyimide precursor in which Y in the general formula (2) is the general formula (4). 3. The method according to claim 1 or 2,
Wherein Y in the general formula (2) is a general formula (5). (a2) a compound represented by the following general formula (10):
[Chemical Formula 6]

And a weight average molecular weight of 30,000 or more and 300,000 or less.
Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ). &Lt; / RTI &gt; R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.} The method according to claim 6,
The polyimide precursor of (a2) wherein the content of molecules having a weight average molecular weight of less than 1,000 in the polyimide precursor is less than 5% by mass. 8. The method according to claim 6 or 7,
The polyimide precursor in which n in the general formula (10) is 0. 6. The method according to any one of claims 1 to 5,
Wherein X ₁ and X ₂ are selected from the group consisting of pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'- Bis (trimellitic acid monoester acid anhydride) (TAHQ), which is a tetravalent organic group derived from at least one species selected from the group consisting of bis (trimellitic acid monoester acid anhydride) (TAHQ). A resin composition comprising the polyimide precursor according to any one of claims 1 to 9 and (b) an organic solvent. 11. The method of claim 10,
Further, a resin composition comprising at least one member selected from the group consisting of (c) a surfactant, and (d) an alkoxysilane compound. (11): &lt; EMI ID =
(7)

(Wherein X ₁ and X ₂ represent a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4. Y is at least one member selected from the group consisting of the following general formulas (3), (4) and (5). l and m each independently represent an integer of 1 or more and satisfy 0.01? 1 / (1 + m)? 0.99.
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(In the formulas, R ₄ to R ₁₁ each independently represent a monovalent organic group having 1 to 20 carbon atoms. d ~ k is an integer from 0 to 4.} (12): &lt; EMI ID =
(11)

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ). &Lt; / RTI &gt; R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4, and the elongation is 15% or more. A step of forming a coating film by applying the resin composition according to claim 10 or 11 on a surface of a support,
A step of forming a polyimide resin film by imidizing the polyimide precursor contained in the coating film by heating the support and the coating film;
And peeling the polyimide resin film from the support. 15. The method of claim 14,
Wherein the step of irradiating the support with a laser is performed prior to the step of peeling the polyimide resin film from the support. A step of forming a coating film by applying the resin composition according to claim 10 or 11 on a surface of a support,
And heating the support and the coating film to imidize the polyimide precursor contained in the coating film to form a polyimide resin film. A step of forming a coating film by applying the resin composition according to claim 10 or 11 on a surface of a support,
A step of forming a polyimide resin film by imidizing the polyimide precursor contained in the coating film by heating the support and the coating film;
Forming a device or a circuit on the polyimide resin film;
And peeling the polyimide resin film on which the element or circuit is formed from the support. (12): &lt; EMI ID =
[Chemical Formula 12]

Wherein X ₃ is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic acid dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester acid anhydride ) (TAHQ), and R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}
Wherein the polyimide film is a polyimide film. (13): &lt; EMI ID =
[Chemical Formula 13]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b and c are integers of 0 to 4, and a low-temperature polysilicon TFT layer. Characterized in that the degree of yellowness at a thickness of 10 microns after heating at 400 DEG C or higher is 20 or less and the absorbance at 308 nm is 0.6 or more and 2.0 or less when the film thickness is 0.1 micron and the elongation is 15% Polyimide film. (a) a polyimide precursor represented by the following general formula (1)
(b) an organic solvent,
(c) a surfactant, and (d) an alkoxysilane compound.
[Chemical Formula 14]

Wherein X ₁ represents a tetravalent group having 4 to 32 carbon atoms. R ₁ , R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1; And a, b, and c are integers from 0 to 4.}

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