KR101946092B1

KR101946092B1 - Resin composition, and film formation method using same

Info

Publication number: KR101946092B1
Application number: KR1020147011045A
Authority: KR
Inventors: 다카후미 시미즈; 신타로 후지토미; 노부유키 미야키; 유이치 에리야마
Original assignee: 제이에스알 가부시끼가이샤
Priority date: 2011-09-29
Filing date: 2012-09-24
Publication date: 2019-02-08
Also published as: CN103842409A; JP5862674B2; WO2013047451A1; TWI577734B; JPWO2013047451A1; KR20140069264A; TW201315772A

Abstract

The present invention relates to a resin composition comprising a polyimide precursor having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and a solvent comprising a non- will be.

(In the formula (1), R represents independently a hydrogen atom or a monovalent organic group, R ¹ independently represents a divalent organic group, R ² independently represents a tetravalent organic group, and n represents a positive integer , Provided that at least one of R ¹ and R ² includes a halogen atom or a halogenated alkyl group)

(2), a plurality of R ^{5 s} each independently represent a monovalent organic group having 1 to 20 carbon atoms, and m represents an integer of 3 to 200)

Description

RESIN COMPOSITION AND FILM FORMATION METHOD USING SAME [0002]

The present invention relates to a resin composition and a film forming method using the resin composition.

In general, all aromatic polyimides obtained from aromatic tetracarboxylic acid dianhydrides and aromatic diamines have excellent heat resistance and mechanical properties owing to the rigidity of the molecule, the point where the molecule is stabilized in resonance, the point of strong chemical bonding, and the like The polyimide or polyimide composition is widely used as a raw material for films, coatings, molded parts and insulating materials in fields such as electric, battery, automobile and aerospace industries.

However, when the above-mentioned conventional polyimide-forming composition is used to form a film on a support such as a glass substrate, it is pointed out that the substrate or the film itself is warped due to shrinkage and deformation during film formation.

Here, Patent Document 1 discloses a polyimide precursor resin composition for a flexible device substrate comprising a polyimide precursor synthesized from p-phenylenediamine and s-biphenyltetracarboxylic dianhydride.

In addition, the resin composition can be formed by coating on a carrier substrate such as a glass substrate, can be formed into a polyimide film having excellent heat resistance and low thermal expansion coefficient, and does not cause peeling from the carrier substrate during the formation of circuits and the like , And can be cleanly peeled off from the glass substrate.

Japanese Patent Application Laid-Open No. 2010-202729

However, in the conventional resin composition containing a polyimide precursor, when the composition is coated on a support such as a glass substrate to form a film, the drying speed is slow and the productivity is low.

Disclosure of the Invention An object of the present invention is to provide a thermosetting resin composition which is excellent in storage stability, has an excellent productivity due to a high drying speed, is excellent in adhesion and releasability to a substrate, has a high glass transition temperature, And to provide a resin composition and a film forming method capable of easily producing an excellent film.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a polyimide precursor (polyamic acid) having a specific structural unit and a solvent containing a non- And finally completed the present invention.

That is, the present invention provides the following [1] to [9].

[1] A resin composition comprising a polyimide precursor having a structural unit represented by the following formula (2) and having a structural unit represented by the following formula (1), and a solvent comprising a non-amide-based solvent as a main component.

[2] The resin composition according to [1], wherein the R ¹ includes a group selected from the group represented by the following formula (3).

(3), R ³ is independently a group containing an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group or a siloxane group, a hydrogen atom, a halogen atom, an alkyl group, A nitro group, a cyano group or a sulfo group, and the hydrogen atom of the alkylene group and any hydrogen atom of the alkyl group may be substituted with a halogen atom, provided that at least one of the plurality of R ³ contained in one group is a halogen atom Or a halogenated alkyl group, a1 represents an integer of 1 to 3, a2 represents 1 or 2, a3 independently represents an integer of 1 to 4, and e represents an integer of 0 to 3)

[3] The resin composition according to [1] or [2], wherein the solvent is a mixed solvent comprising two or more kinds of solvents.

[4] The resin composition according to [3], wherein the solvent comprises 20% by weight or more of a solvent having the highest boiling point in the mixed solvent, based on 100% by weight of the total amount of the mixed solvent.

[5] The resin composition according to any one of [1] to [4], wherein the polyimide precursor has a weight average molecular weight of 10,000 to 1,000,000.

[6] The resin composition according to any one of [1] to [5], wherein the concentration of the polyimide precursor in the resin composition is 3 to 60 mass%.

[7] The resin composition according to any one of [1] to [6], wherein the viscosity measured by an E-type viscometer (25 ° C) is in the range of 500 to 50000 mPa · s.

[8] The resin composition according to any one of [1] to [7], which is for forming a film.

[9] A process for producing a resin composition, comprising the steps of: applying a resin composition according to any one of [1] to [8]

A step of evaporating the solvent from the coating film,

A step of imidizing the polyimide precursor

&Lt; / RTI >

The resin composition according to the present invention is excellent in storage stability and has excellent transparency and mechanical strength according to the composition and has a high glass transition temperature and is capable of easily producing a film having little occurrence of warping and cloudiness in a short time, can do.

Further, according to the resin composition of the present invention, when a resin composition is applied to a substrate such as a glass substrate to form a film, a film having excellent adhesion to the substrate and excellent peelability can be easily formed.

&Lt; Resin composition &

The resin composition of the present invention comprises a polyimide precursor having a structural unit represented by the following formula (2) and having a structural unit represented by the following formula (1), and a solvent containing a nonimide-based solvent as a main component.

Since the resin composition of the present invention comprises the polyimide precursor and the non-amide solvent, the film having a high glass transition temperature, less occurrence of warpage and less turbidity and having excellent mechanical strength can be easily produced in a short time with good productivity When a resin composition is applied to a substrate such as a glass substrate to form a film, a film having excellent adhesion to the substrate and excellent peelability can be easily formed.

In the present invention, the term " adhesion " means that the film (film) and the substrate are bonded to each other when a film is formed on the substrate, or when a device for producing wiring, Refers to a property that the film can be peeled off from the substrate when the film is to be peeled off from the substrate (when a force for peeling the film from the substrate is applied) with less peeling-off property .

The polyimide precursor has a structural unit represented by the following formula (2) and a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1)"). Therefore, the polyimide obtained from the precursor has a flexible skeletal site including a rigid skeleton site and a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)") It is believed that the microparticles form a microphase separation structure in which the site is marine and the flexible skeleton site is islands. It is believed that the polyimide forms the micro-phase separated structure, whereby a film with reduced residual stress is obtained.

Also, in the present invention, microphase separation means that island portions including a flexible skeleton portion in a sea portion including an upright skeleton portion are dispersed in a size of about 1 nanometer to 1 micrometer.

The term " warpage " refers to the rounding of the film judged by the naked eye, and " residual stress " refers to the stress remaining in the film after the resin composition is coated on a substrate such as a glass substrate to form a film, It becomes a standard of "warpage" that can occur. Specifically, it can be measured by the method described in the following examples.

In the above formula (1), R is independently a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, R ¹ independently represents a divalent organic group, and R ² independently represents a tetravalent organic group. n represents a positive integer, preferably an integer of 1 to 2500.

Further, at least one of R ¹ and R ² includes a halogen atom or a halogenated alkyl group. Herein, "R ¹ includes a halogen atom (fluorine atom)" means, for example, a case where R ¹ is a group such as -CH ₂ -CHF-CH ₂ -, "R ¹ represents a halogenated alkyl group (fluorinated alkyl group) Means, for example, a case where R ¹ is a group such as -CH ₂ -CH (CF ₃ ) -CH ₂ -.

Since the structural unit (1) contains a halogen atom or a halogenated alkyl group, a polyimide precursor having excellent solubility can be obtained, and a polyimide excellent in heat resistance can be obtained from the precursor.

In the formula (2), a plurality of R ^{5 s} each independently represent a monovalent organic group having 1 to 20 carbon atoms, and m represents an integer of 3 to 200.

The monovalent organic group represented by R in the formula (1) is preferably a monovalent organic group having 1 to 20 carbon atoms. The " carbon number of 1 to 20 " represents " carbon number of 1 or more and carbon number of 20 or less ". The same description in the present invention has the same meaning.

Examples of the monovalent organic group having 1 to 20 carbon atoms for R include a monovalent hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms and specific examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, And the like.

The divalent organic group represented by R ¹ in the above formula (1) is preferably a divalent organic group having 1 to 40 carbon atoms.

As the divalent organic group having 1 to 40 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 40 carbon atoms is preferable, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable. When two or more ring structures are included in the organic group, there may be mentioned a polycyclic structure in which one or more rings share a bond, a spiro hydrocarbon structure, and a structure in which a ring and a ring, such as biphenyl, . Examples of the bonding group include an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group and a siloxane group in addition to the single bond. When the divalent organic group includes a hydrogen atom, any hydrogen atom may be substituted with a halogen atom.

The bivalent organic group preferably contains a group selected from the group represented by the following formula (3), and more preferably a group selected from the group represented by the following formula (3). When the divalent organic group in R ¹ is a group selected from the group represented by the following formula (3), the sea portion has a structure having a more rigid skeleton. Therefore, it is preferable because a residual stress is small and a film in which warpage is suppressed can be obtained.

In the formula (3), R ³ independently represents a group containing an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group or a siloxane group, a hydrogen atom, a halogen atom, an alkyl group, A cyano group or a sulfo group, and the hydrogen atom of the alkylene group and the alkyl group may be substituted with a halogen atom. Provided that at least one of the plurality of R < ³ > included in one group contains a halogen atom or a halogenated alkyl group. a1 represents an integer of 1 to 3, a2 represents 1 or 2, a3 independently represents an integer of 1 to 4, and e represents an integer of 0 to 3.

Examples of the group containing ether bond, thioether group, ketone group, ester bond, sulfonyl group, alkylene group, amide group or siloxane group include ether bond, thioether group, ketone group, ester bond, sulfonyl group, alkylene group, amide Or an organic group having 1 to 10 carbon atoms containing a siloxane group.

In the above formula (3), R ³ preferably contains from 1 to 12 halogen atoms, and from 3 to 8, in view of being able to easily produce a film having excellent mechanical strength in a short time with good productivity .

In the present invention, when R ³ is a halogen atom, it is said that "one halogen atom is contained" and when R ³ is, for example, a trifluoromethyl group, "there are three halogen atoms".

Examples of the halogenated alkyl group in R ³ in the above formula (3) include a methyl group substituted with a halogen atom or an alkyl group having 2 to 20 carbon atoms.

The halogenated alkyl group having 2 to 20 carbon atoms is preferably an alkyl group having 2 to 10 carbon atoms substituted with a halogen atom, and examples thereof include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, And a group in which any hydrogen atom of the actual group is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The halogenated alkyl group in R ³ in the above formula (3) is preferably an alkyl group having 1 to 2 carbon atoms substituted with a halogen atom, and specifically, any hydrogen atom of the methyl group or ethyl group is preferably a fluorine atom, a chlorine atom, And an atom-substituted group.

The halogen atom and the halogen atom contained in the halogenated alkyl group in R ³ in the above formula (3) are preferably a fluorine atom in view of being able to easily produce a film having excellent mechanical strength in a short time with good productivity .

As R ³ which does not contain a halogen atom, a hydrogen atom, an alkyl group, a fluorene group, a hydroxy group, a nitro group, a cyano group or a sulfo group is preferable, and a hydrogen atom or an alkyl group is more preferable.

The alkyl group in R ³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, A butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.

Examples of the group containing an alkylene group in R ³ in the above formula (3) include a methylene group or an alkylene group having 2 to 20 carbon atoms, and any hydrogen atom of the alkylene group may be substituted with a halogen atom.

The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and an isopropylidene group. have.

e is preferably an integer of 0 to 2, more preferably 0 or 1, and more preferably 0.

a1 is preferably 1 or 3, a2 is preferably 2, and a3 is preferably 1 or 2, more preferably 1.

The divalent organic group represented by R ¹ in the above formula (1) is preferably a group selected from the group represented by the following formula (3 ').

In the formula (3 '), R ³ is R ³ and motion independently of the general formula (3).

Examples of the group represented by the formula (3 ') include groups selected from the group consisting of the following formulas (3'-1) and (3'-2).

The divalent organic group represented by R ¹ in the above formula (1) is more preferably a group selected from the group represented by the following formula (3 ").

The tetravalent organic group represented by R ² in the above formula (1) is preferably a tetravalent organic group having 1 to 40 carbon atoms.

As the tetravalent organic group having 1 to 40 carbon atoms, a tetravalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 40 carbon atoms is preferable. When two or more ring structures are included in the organic group, there may be mentioned a polycyclic structure in which one or more rings share a bond, a spiro hydrocarbon structure, and a structure in which a ring and a ring, such as biphenyl, . Examples of the bonding group include an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group and a siloxane group in addition to the single bond.

R ² is more preferably a group selected from the group represented by the following formula (4), and more preferably a group selected from the group represented by the following formula (4 '). When the tetravalent organic group in R ² is a group selected from the group selected from the group represented by the following formula (4), particularly the group represented by the following formula (4 '), the polyimide obtained from the polyimide precursor has a rigid The structure having a skeleton is easy to form, and a micro-phase separation structure can be easily formed, so that a residual stress is small and a film in which the occurrence of warpage is suppressed can be obtained.

In the formula (4), R ⁴ is independently a group containing an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group or a siloxane group; A hydrogen atom; A halogen atom; An alkyl group; A hydroxy group; A nitro group; Cyano; Or a sulfo group, and the hydrogen atom of the group containing the alkylene group and the alkyl group may be substituted with a halogen atom. D represents an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group or a siloxane group, b independently represents 1 or 2, c independently represents an integer of 1 to 3, f represents an integer of 0 to 3;

It is preferable that at least one of the plurality of R ⁴ included in one group contains a halogen atom or a halogenated alkyl group.

R ⁴ in the above formula (4) preferably contains 1 to 12 halogen atoms, and it is preferable that R ⁴ in the formula (4) contains 3 to 8 from the viewpoint of easily producing a film having excellent mechanical strength in a short time, Is more preferable.

Examples of the halogenated alkyl group in R ⁴ in the above formula (4) include a methyl group substituted with a halogen atom or an alkyl group having 2 to 20 carbon atoms.

The halogenated alkyl group in R ⁴ in the above formula (4) is preferably an alkyl group having 1 to 2 carbon atoms substituted with a halogen atom, and specifically, any hydrogen atom of the methyl group or ethyl group is preferably a fluorine atom, a chlorine atom, And an atom-substituted group.

The halogen atom and the halogen atom contained in the halogenated alkyl group in R ⁴ in the formula (4) are preferably a fluorine atom in view of being able to easily produce a film having excellent mechanical strength in a short time with good productivity.

As R ⁴ which does not contain a halogen atom, a hydrogen atom, an alkyl group, a fluorene group, a hydroxy group, a nitro group, a cyano group or a sulfo group is preferable, and a hydrogen atom or an alkyl group is more preferable.

The alkyl group in R ⁴ in the above formula (4) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, An isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.

Examples of the group containing an alkylene group in R ⁴ in the above formula (3) include a methylene group or an alkylene group having 2 to 20 carbon atoms, and any hydrogen atom of the alkylene group may be substituted with a halogen atom.

D is preferably an ether group, a thioether group or a sulfonyl group.

As c, 1 or 2 is preferable.

f is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

The group selected from the group represented by the formula (4) is preferably a group selected from the group represented by the following formula (4 ').

The structural unit (1) includes the structural unit (2). The structural unit (2) may be contained in at least one group selected from the group consisting of a plurality of R ¹ and R ² in the structural unit (1), and may be included at the end of the structural unit (1) Is preferably included in at least one group selected from the group consisting of R < ¹ > and R < ² >. Further, "at least one group selected from the group consisting of a plurality of R ¹ and R ² includes a structural unit represented by the following formula (2)" means that when n is 2 or more, R ¹ and R ² are each 2 Is present in at least one structural unit (1), and at least one of the plurality of R ¹ and R ² includes a structural unit represented by the following formula (2).

Since the polyimide precursor includes the structural unit (2), a resin composition containing the precursor can provide a film having a small residual stress and suppressing the occurrence of warpage.

Examples of the monovalent organic group having 1 to 20 carbon atoms in R ⁵ in the above formula (2) include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent alkoxy group having 1 to 20 carbon atoms.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ⁵ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms and specifically includes a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, And practical training.

The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.

The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group and a naphthyl group.

Examples of the monovalent alkoxy group having 1 to 20 carbon atoms in R ⁵ include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group and a cyclohexyloxy group.

Wherein at least one of the plurality of R < ⁵ > s in the formula (2) includes an aryl group, the islands including the flexible skeleton region are excellent in affinity with the sea portion including the rigid skeleton region, (Uniformly) dispersed (micro-phase separation) to a size of about nanometer to 1 micrometer. More specifically, the plurality of R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms. In this case, the ratio of the number of moles (i) of the alkyl group having 1 to 10 carbon atoms in the R ⁵ in the structural unit (2) to the number of moles (ii) of the aryl group having 6 to 12 carbon atoms, provided that (i) + (ii) = 100) is preferably (i) :( ii) = 90 to 10: 10 to 90, more preferably (i) :( ii) = 85 to 15:15 to 85, i) :( ii) = 85 to 65: 15 to 35. [ If the ratio of the number of moles (i) of the alkyl group to the number of moles (ii) of the aryl group in all the R ⁵ in the structural unit (2) is out of the above range, the obtained polyimide may fail to form a micro phase separation structure. When the ratio of the number of moles of alkyl group (i) to the number of moles of aryl group (ii) is in the above range, microphase separation (skeletal sites including structural unit (2) is nano-dispersed) becomes possible and low coefficient of linear expansion and low Residual stress and the like, which is excellent in transparency and is not easily clouded.

The alkyl group having 1 to 10 carbon atoms is preferably a methyl group, and the aryl group having 6 to 12 carbon atoms is preferably a phenyl group.

When the total amount of the polyimide precursor is 100 mass%, the content of the structural unit (2) is preferably 5 to 40 mass%, more preferably 5 to 23 mass%, and more preferably 8 to 22 mass% , More preferably from 9.5 to 21 mass%.

When the proportion of the structural unit (2) contained in the polyimide precursor exceeds the above range, when the resin composition of the present invention is applied to a substrate such as a glass substrate to form a coating film, the formed coating film is peeled off from the substrate It tends to become difficult. When the amount of the structural unit (2) contained in the polyimide precursor is less than the above range, when the resin composition of the present invention is applied to a substrate such as a glass substrate to form a coating film, the residual stress of the formed coating film increases , There is a possibility that warpage may occur in the film obtained when the coating film is peeled from the substrate.

M in the above formula (2) is an integer of 3 to 200, preferably 10 to 200, more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably 35 to 80. When m is less than 2, the polyimide obtained from the polyimide precursor may be difficult to form a micro phase separation structure. When m is more than 200, the size of the island including the skeletal part including the structural unit (2) Exceeds 1 mu m, the coating film may become opaque or the mechanical strength may be lowered.

The polyimide precursor preferably contains 60 mass% or more, more preferably 77 mass% or more, and further preferably 79 mass% or more of the structural unit (1) in 100 mass% of the polyimide precursor. When the ratio of the structural unit (1) in the polyimide precursor is in the above range, a film having a small residual stress and hardly causing warping can be obtained.

The inclusion of 60 mass% or more of the structural unit (1) in 100 mass% of the polyimide precursor means that the structural unit -NH-R ¹ -NH-, the structural unit -NH-R ¹ -NH ₂ , the structural unit CO -R ^₂ (COOR) ² -CO-, structural units ^{_{-CO-R 2 (COOR) 2}} -COOH, the structural unit (2), and the structural units ^{_{- (Si (R 5) 2}} -O) m -Si (R ⁵⁾ ₂ -R ¹⁰ is the sum of the R ^1, R ^2, and the structural unit comprising a structural unit (2) -R ^11, such means is not less than 60% by weight (and, R ^1, R ^2, and R is the formula (1) in a R ^1, R ^2, and R and copper, R ⁵ is R ¹⁰ of R is ⁵ and the accept, R ¹⁰ and R ¹¹ is the formula (7 ') and (8') in the formula (2) And R ¹¹ ).

Further, the polyimide precursor may have a part of the structural unit (1) imidized.

In the structural unit (1), R ¹ is the formula (3) a group selected from the group represented by is a group in particular selected from the group represented by the formula (3 '), R ² is Formula (4) (4 '), and when m in the formula (2) is 3 or more, the polyimide obtained from the polyimide precursor has a higher selectivity than the microphase The separation structure can be easily taken, and therefore, it is particularly preferable in view of reduction of the residual stress of the obtained film.

The polyimide precursor may contain, in addition to the structural unit contained in the above formula (1), an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide (Hereinafter also referred to as " structural unit (56) ") derived from a monomer (hereinafter also referred to as " monomer (I) ") containing at least one kind of group selected from the group consisting of a hydroxyl group and a siloxane group .

Examples of the alkylene group include the same groups as the alkylene group in R ³ in the formula (3).

In addition, the "structural units contained in the formula (1)" refers to the structural units -NH-R ¹ -NH-, structural units -NH-R ¹ -NH _2, structural units ^{_{-CO-R 2 (COOR) 2}} - CO-, a structural unit -CO-R ² (COOR) ₂ -COOH, a structural unit (2), and a structural unit- (Si (R ⁵ ) ₂ -O) _m -Si (R ⁵ ) ₂ -R ¹⁰ -R ^11, etc. of R ^1, R ^2, and the structural unit (2) refers to a structural unit containing (and, R ^1, R ^2, and R is R ^1, R ^2, and R and copper in the formula (1), R ⁵ is R ⁵ as agreed in the formula (2), R ¹⁰ and R ¹¹ is R ¹⁰ and R ¹¹ is to accept and in the formula (7 ') and (8')).

The structural unit (56) contains a group represented by R ¹ and R ² in the structural unit (1), which is contained in the main chain of the polyimide precursor, and a tetracarboxylic acid dianhydride And derivatives thereof or imino-forming compounds.

The main chain of the polyimide precursor means a chain containing R ¹ or R ² of the structural unit (1). For example, -COOR in the structural unit (1) is not a main chain but a side chain.

When the structural unit (56) is contained in the polyimide precursor, the coefficient of linear expansion of the obtained film is increased, and a film capable of elongation is obtained as required.

Increasing the content of the structural unit (56) and / or the content of the structural unit (2) in the polyimide precursor increases the coefficient of linear expansion of the obtained film. Therefore, the resin composition The blending amount of the structural unit 56 and / or the structural unit 2 can be changed according to these substrates. Specifically, since the coefficient of linear expansion of Cu is 16.8 ppm / K, when the resin composition of the present invention is applied onto a substrate containing Cu, the polyimide precursor preferably includes the structural unit (56) It is preferable that the polyimide precursor does not contain the structural unit (56) when the resin composition of the present invention is applied on a substrate containing Si. In addition, since the coefficient of linear expansion of chromium is 8.2 ppm / K, the coefficient of linear expansion of glass is 9 ppm / K, the coefficient of linear expansion of stainless steel SUS430 is 10.4 ppm / K, and the coefficient of linear expansion of nickel is 12.8 ppm / K. , The polyimide precursor preferably contains 0 to 15 mass% of the structural unit (56) in 100 mass% of the polyimide precursor.

The monomer (I) is preferably a compound represented by the following formula (5) (hereinafter also referred to as "compound (5)") or a compound represented by the formula (6) .

In the formulas (5) and (6), each A independently represents an ether bond (-O-), a thioether group (-S-), a ketone group (-C (= O) -, a sulfonyl group (-SO ₂ -), an alkylene group (-R ⁷ -), an amide group (-C (═O) -NR ⁸ -), a siloxane group (-Si (R ⁹ ) ₂ -O-Si (R ⁹ ) ₂ -) and a fluorene group, and R ⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group or a nitro group, and any hydrogen atom May be substituted with a halogen atom. d independently represents an integer of 1 to 4;

Each of R ⁸ and R ⁹ independently represents a hydrogen atom, an alkyl group or a halogen atom, and the hydrogen atom of the alkyl group may be substituted with a halogen atom. Examples of the alkyl group for R ⁶ , R ⁸ and R ⁹ include the same groups as the alkyl group for R ³ in the above formula (3). The halogen atom is preferably a chlorine atom or a fluorine atom.

The A is preferably an ether bond, and the R ⁶ is preferably a hydrogen atom.

Examples of the alkylene group (-R ⁷ -) in A in the formulas (5) and (6) include the same groups as the alkylene group in R ³ in the formula (3) An isopropylidene group and a hexafluoroisopropylidene group are preferable.

Examples of the compounds (5) and (6) include the compounds described in the following group of compounds (5-1) to (6-9).

When the polyimide precursor includes the structural unit (56), the polyimide precursor preferably contains 0 to 15 mass%, more preferably 0 to 10 mass% of the structural unit (56) in 100 mass% of the polyimide precursor By mass, more preferably 0 to 9% by mass, and particularly preferably 0 to 8% by mass.

If the content of the structural unit (56) exceeds 15% by mass, the elasticity of the rigid skeleton portion becomes low, and it becomes difficult to shift the residual stress to the flexible skeleton portion, so that warpage tends to occur in the obtained film.

When the content of the structural unit (56) is in the above range, it is possible to obtain a film that is liable to elongate while suppressing the occurrence of warpage.

When the polyimide precursor includes the structural unit (56), the polyimide precursor containing the structural unit (56) is preferably a polyimide precursor having (i) a structural unit represented by R ¹ or R ² in the formula (1) ), And (ii) the polyimide precursor is represented by a structure in which the structural unit (56) is contained in a portion other than the structural unit (1). In the case of (i) above, when the polyimide precursor includes a structural unit derived from the compound (5) in R ¹ in the above formula (1), the polyimide precursor may be, for example, Is displayed. In this case, " the structural unit (56) preferably contains 0 to 15 mass% in 100 mass% of the polyimide precursor " means that in 100 mass% of the polyimide precursor, Means that it contains 0 to 15 mass% of a structural unit represented by the embedded structure (including -NH- at both ends).

In the case of (i), the structural unit (56) may be contained in at least one group selected from the group consisting of a plurality of R ¹ and R ² in the structural unit (1) May also be included at the end.

The general formula (5A) wherein an R, R ¹ and R ² are each independently selected from R, R ¹ and R ² as agreed in the formula (1), A, R ⁶ and d are the above formula (5) are each independently and in a, R ⁶ and d and consent, n1 + n2 is an n and copper in the formula (1).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 10,000 to 1,000,000, more preferably 10,000 to 200,000, and still more preferably 20,000 to 150,000. The number average molecular weight (Mn) is 5,000 to 10,000,000, preferably 5,000 to 500,000, and particularly preferably 15,000 to 200,000.

If the weight average molecular weight or the number average molecular weight of the polyimide precursor is less than the above lower limit, the strength of the resulting film may be lowered. In addition, the coefficient of linear expansion of the resulting film may rise to more than necessary. On the other hand, when the weight average molecular weight or the number average molecular weight of the polyimide precursor exceeds the upper limit, the viscosity of the resin composition becomes high. Therefore, when the resin composition is applied to a substrate such as a glass substrate to form a film, The amount of the polyimide precursor that can be obtained is decreased, and the film thickness precision such as the flatness of the obtained coating film may be deteriorated.

The molecular weight distribution (Mw / Mn) of the polyimide precursor is preferably 1.0 to 10.0, more preferably 1.5 to 5.0, and particularly preferably 1.5 to 4.0.

The weight average molecular weight, the number average molecular weight, and the molecular weight distribution were measured by using a HLC-8220 type GPC apparatus (guard column: TSK guard colomn ALPHA column: TSKgel ALPHA-M manufactured by TOSOH, N-methylpyrrolidone (NMP) As shown in Fig.

&Lt; Synthesis method of polyimide precursor >

The polyimide precursor having the structural unit (1) is preferably a component comprising at least one acyl compound selected from the group consisting of a tetracarboxylic acid dianhydride and a reactive derivative thereof (hereinafter referred to as " component (A) ) And an imino-forming compound (hereinafter also referred to as "component (B)"). However, in the synthesis of the polyimide, it is preferable to use a compound containing the structural unit (2).

According to this reaction, it is possible to obtain a polyimide precursor according to the structure of the starting compound to be used and a polyimide precursor having a structural unit derived from the compound in an amount depending on the amount of the starting compound to be used.

In this case, an acyl compound (hereinafter also referred to as "compound (A-2)") containing a structural unit (2) is used as the component (A) (Hereinafter also referred to as " compound (B-2) ") is preferably used. The compound (A-2) and the compound (B-2) may both be used.

[Component (A)] [

(A) is at least one acyl compound selected from the group consisting of a tetracarboxylic acid dianhydride and a reactive derivative thereof. And preferably at least one compound selected from the group consisting of the compound (A-2) and the acyl compound (A-1) other than the compound (A-2).

Examples of the acyl compound (A-1) include at least one compound selected from the group consisting of an aromatic tetracarboxylic acid dianhydride, an alicyclic tetracarboxylic acid, the compound (6) and reactive derivatives thereof .

Specific examples of the acyl compound (A-1) include 4,4'-oxydiphthalic acid dianhydride, pyromellitic acid dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilanetetracar (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 2,3,4,5-furan tetracarboxylic acid dianhydride, (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoro (2-anilino) -biphenyltetracarboxylic acid dianhydride, bis (phthalic anhydride), bis (3,3'-biphenyltetracarboxylic dianhydride) (Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) dianhydride, Phenylphthalic acid) -4,4'-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride; and reactive derivatives thereof;

Butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxy Cyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,5,6-tricarboxy norbornane-2-acetic acid dianhydride, 2,3,4,5-tetra (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-dihydropyridazinecarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro- c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [ , 2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, and 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride. Carboxylic acid dianhydrides or alicyclic tetracarboxylic acid dianhydrides, and reactive derivatives thereof.

These compounds may be used singly or in combination of two or more.

Examples of the reactive derivative include a tetracarboxylic acid, an acid esterified product of the tetracarboxylic acid, and an acid chloride of the tetracarboxylic acid.

Of these, aliphatic tetracarboxylic acid dianhydrides or alicyclic tetracarboxylic acid dianhydrides are preferably used from the viewpoints of excellent transparency and good solubility in organic solvents. From the viewpoints of heat resistance, low coefficient of linear expansion (dimensional stability), and low absorption (water absorption), aromatic tetracarboxylic acid dianhydrides are preferably used.

The acyl compound (A-1) is a compound having a group selected from the group consisting of the above-mentioned formula (4) or (4 '). The acyl compound (A- (Micro-phase separation structure) at a size of about nanometer to 1 micrometer, so that the stress generated in the film forming process can be efficiently absorbed at the above-mentioned flexible skeleton portion, so that the residual stress is small, Is more preferable in terms of obtaining a suppressed film.

Specific examples of such compounds include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) And these compounds may be used singly or in combination of two or more.

The compounding amount of the compound (A-1) (except for the compounds (6) and (6 ')) is not particularly limited, and when the total amount of the total acyl compound (component (A)) is 100% (A-2) and / or the compound (6) is contained in the component (A), it may be added in an amount of 100% by mass minus the preferable amount of each of these compounds have.

Specific examples of the compound (A-2) include a tetracarboxylic acid dianhydride having a structural unit represented by the formula (2) and at least one acyl compound selected from the reactive derivatives thereof. (Hereinafter also referred to as a compound (7 ')), a compound represented by the following formula (8), a compound represented by the following formula (7) At least one compound selected from the group consisting of a compound represented by the following formula (8) (hereinafter also referred to as "compound (8)") and a compound represented by the following formula (8 ' .

These compounds may be used singly or in combination of two or more.

Examples of the reactive derivative include a tetracarboxylic acid having a structural unit represented by the formula (2), an acid esterified product of the tetracarboxylic acid, and an acid chloride of the tetracarboxylic acid.

In the case where a polyimide precursor in which the structural unit (2) is included in at least one of a plurality of R ² in the structural unit (1) is to be synthesized, it is preferable to use the compound (7) and / or (8) It is preferable to use the compound (7 ') and / or (8') in the case where the polyimide precursor in which the structural unit (2) is included in the terminal of the structural unit (1) is to be synthesized.

In the formula (7), (7 '), (8) and (8'), R ⁵ and m is R ⁵ and m and consent of each independently represent the formula (2). R ¹⁰ independently represents a single bond or a divalent organic group having 1 to 20 carbon atoms. In the formulas (7 ') and (8'), R ¹¹ independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. As the monovalent organic group having 1 to 20 carbon atoms, A group similar to the monovalent organic group having 1 to 20 carbon atoms in R ⁵ , and the like.

Examples of the divalent organic group having 1 to 20 carbon atoms in R ¹⁰ include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms.

The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

The cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.

The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.

The number average molecular weight of the compound (A-2) is preferably 200 to 10,000, more preferably 500 to 10,000, and particularly preferably 500 to 10,000, from the viewpoint of obtaining a film having excellent heat resistance (high glass transition temperature) To 6000. The amine value is preferably 100 to 5000, more preferably 250 to 5,000, and still more preferably 1000 to 3000.

The degree of polymerization (m) in the above-mentioned compounds (7), (7 '), (8) and (8') is the same as in the above formula (2).

In the above formulas (7), (7 '), (8) and (8'), R ⁵ is preferably a methyl group or a phenyl group, and at least one of the plurality of R ⁵ is preferably a phenyl group. When at least one of the plurality of R ⁵ is a methyl group or a phenyl group, and at least one of them is a methyl group, and at least one of them is a phenyl group, the ratio of the mole% The mole ratio of the methyl group to the phenyl group is preferably from 85 to 65, more preferably from 15 to 85:85 to 15, : 15-35. If at least one R ⁵ of the above formulas (7), (7 '), (8) and (8') is not a phenyl group, compatibility of the sea part and the island part is deteriorated, There is a case where a film having a low heat resistance and a low film strength is obtained.

Specific examples of the compound (A-2) include DMS-Z21 (number average molecular weight: 600 to 800, amine value: 300 to 400, m = 4 to 7) manufactured by Gelest Corporation. The compound (A-2) may be used alone or in combination of two or more.

When the compound (A-2) is contained in the component (A), the amount of the compound (A-2) in the case where the total amount of the entire raw material compound (component (A) + component (B) Is preferably from 5 to 40% by mass, more preferably from 5 to 23% by mass, and still more preferably from 8 to 22% by mass, in view of obtaining a film which is excellent in peelability from the substrate and less prone to warpage %, Particularly preferably 9.5 to 21 mass%. The preferable amount of the compound (A-2) is the case where the compound (B-2) is not used in synthesizing the polyimide precursor, and the compound (A- And the compound (B-2) are used, it is preferable that the total amount of the compound (A-2) and the compound (B-2) used is about the same as the compounding amount of the compound (A-2).

The component (A) may also be referred to as a compound (6) and / or a compound represented by the following formula (6 ') (hereinafter also referred to as a "compound (6')" ) May be included. When a polyimide precursor containing the structural unit (56) is contained in the main chain (excluding the terminal) of the polyimide precursor, it is preferable to use the compound (6), and the polyimide precursor In the case of synthesizing a polyimide precursor containing the unit (56), it is preferable to use the compound (6 ').

These compounds may be used singly or in combination of two or more.

In the above formula (6 '), A is the same as A in the above formulas (5) and (6), and R ¹² represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as the monovalent organic group having 1 to 20 carbon atoms represented by R ⁵ in the above formula (2).

When the total amount of the entire raw material compound (component (A) + component (B)) is 100% by mass, when the component (A) contains the compound (6) and / The compounding amount of the compound (6) and the compound (6 ') is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 10% by mass in view of obtaining a film, 9% by mass, and particularly preferably 0% by mass to 8% by mass. However, the preferable amount of the compound (6) and the compound (6 ') is that when the polyimide precursor is synthesized, the compound (5) and / or the compound (5' The compound (6), the compound (6 ') and the compound (5') are used in the case of using the compound (6) and / or the compound (6 ') and the compound 5) and the compound (5 ') is the same as the preferable amount of the compound (6) and the compound (6').

[Component (B)] [

(B) is an imino-forming compound. The term "imino-forming compound" as used herein refers to a compound which reacts with the component (A) to form an imino (group), and specifically includes a diamine compound, a diisocyanate compound, a bis (trialkylsilyl) .

The component (B) preferably includes at least one compound selected from the group consisting of the compound (B-2) and the imino-forming compound (B-1) other than the compound (B-2).

Examples of the compound (B-1) include at least one compound selected from the aromatic diamine group and the compound (5).

Examples of the compound (B-1) include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'- (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl (o- , 2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 3,3'-diethyl-4,4'- diaminobiphenyl, 2,2'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB), 4,4'- Diamino-2,2'-bis (trifluoroacetyl) biphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'- Bis (4-aminophenoxyethoxy) ethane, 9,9-bis (4-aminophenoxy) 1-aminophenyl) fluorene, 9,9-bis (4-aminophenoxyphenyl) fluorene, 5 (6) (TPE-Q), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene APB), 2,5-bis (4-aminophenoxy) biphenyl (P-TPEQ), 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'- Bis (4-aminophenoxyphenyl)] propane, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, bis [4- Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Dimethoxy-4,4-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro- 4,4'-diaminobiphenyl, 4,4'-methylene-bis (2-chloroaniline), 2,2'-difluoro-4,4'-diamino-5,5'- Phenyl, 2,2 ' 4,4'-diaminobiphenyl, 4,4'-methylene-bis (2-fluoroaniline), 9,10-bis (4-aminophenyl) anthracene, o- Tolyl sulfone and the like. These aromatic diamines may be used singly or in combination of two or more.

The compound (B-1) is preferably a compound having a group selected from the group represented by the above-mentioned formulas (3), (3 '), (3'-1) to (3'- , It is possible to disperse the flexible skeleton portion in the sea portion having a high elastic modulus in a very small size of about 1 nanometer to 1 micrometer (uniformly dispersed), so that the stress generated in the film forming process It is preferable from the viewpoint of obtaining a film in which occurrence of warpage is suppressed due to a small residual stress because it can be efficiently absorbed at a flexible skeleton site. Specific examples of such compounds include 4,4'-diamino-2,2 ' -Bis (trifluoromethyl) biphenyl (TFMB), 4,4'-diamino-2,2'-bis (trifluoroethyl) biphenyl, 4,4'-diamino- Bis (trifluoroacetyl) biphenyl, etc. Among them, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl di Preferable.

The compounding amount of the compound (B-1) (excluding the compounds (5) and (5 ')) is not particularly limited, and the total amount of the imide-forming compound (component (B)) is 100% (B-2) and / or the compound (5) is contained in the component (B), the amount of the compound (B-2) and / or the compound You may.

The compound (B-2) is not particularly limited as long as it is an imino-forming compound containing the structural unit (2), but preferably a compound represented by the following formula (9) And a compound represented by the following formula (9 ') (hereinafter also referred to as "compound (9')").

In the case where the polyimide precursor in which the structural unit (2) is included in at least one group selected from the group consisting of a plurality of R ¹ and R ² in the structural unit (1) is to be synthesized, the compound (9) , And when it is desired to synthesize the polyimide precursor contained in the terminal of the structural unit (1), the compound (9 ') is preferably used.

These compounds may be used singly or in combination of two or more.

Formula (9) and (9 ') of, R ⁵ and m are each, and R ⁵ and m and consent of independently the general formula (2), R ¹⁰ are each independently selected from the formula (7), (7') , 8 and 8 'and R ¹⁰ in the accept, R ¹¹ are each independently selected from the formula (7' is R ¹¹ with the consent of) and (8 ').

As the compound (B-2), it is possible to finely disperse the flexible skeleton portion in a size of about nanometers to micrometers in the sea portion including the rigid skeleton portion, so that the heat resistance (high glass transition temperature) From the viewpoint of obtaining an excellent film, the number average molecular weight is preferably 500 to 12,000, more preferably 1,000 to 8,000, and still more preferably 3,000 to 6,000. The amine value is preferably 250 to 6,000, more preferably 500 to 4,000, and still more preferably 1,500 to 3,000.

The degree of polymerization (m) in the above formulas (9) and (9 ') is the same as in the above formula (2), and the preferable range is also the same.

In the above formulas (9) and (9 '), R ⁵ is preferably a methyl group or a phenyl group, and at least one of the plurality of R ⁵ is preferably a phenyl group. When at least one of the plurality of R ⁵ is a methyl group or a phenyl group, and at least one of them is a methyl group, and at least one of them is a phenyl group, the ratio of the mole% The mole ratio of the methyl group to the phenyl group is preferably from 85 to 65, more preferably from 15 to 85:85 to 15, : 15-35. If at least one of R < ⁵ > in the above formulas (9) and (9 ') is not a phenyl group, the compatibility of the sea portion and the island portion is deteriorated and the dispersion size of the island portion exceeds 1 micrometer, A film may sometimes be obtained.

(Number average molecular weight: 4,400, degree of polymerization (m) = 41, phenyl group: methyl group = 25: 75mol (trade name) manufactured by Shin-Etsu Chemical Co., X22-161A (number average molecular weight 1,600, degree of polymerization (m) = 20), X22-161B (number average molecular weight: 1,300) (Number average molecular weight: 900, degree of polymerization (m) = 11), KF-8012 (number average molecular weight: 4400, degree of polymerization (m) = 58), BY16-835U ) And the like. The imino-forming compound (B-2) may be used singly or in combination of two or more. The degree of polymerization (m) can be calculated, for example, by the following equation (in the case where both ends are aminopropyl groups, in the case of a compound wherein all of R ^{5 in} the above formula (2) is a methyl group or a phenyl group).

m = (number average molecular weight - molecular weight of both end groups (aminopropyl group) 116.2) / (74.15 x mol% x methyl group + 0.01 + 198.29 x mol% x phenyl group)

When the total amount of the entire raw material compound (component (A) + component (B)) is 100 mass%, the amount of the compound (B-2) Is preferably from 5 to 40% by mass, more preferably from 5 to 23% by mass, still more preferably from 8 to 22% by mass, in view of obtaining a film which is excellent in peelability from the substrate and hardly causes warpage %, Particularly preferably 9.5 to 21 mass%. However, the preferable amount of the compound (B-2) is an amount when the compound (A-2) is not used in synthesizing the polyimide precursor.

The component (B) may also be referred to as a compound (5) and / or a compound represented by the following formula (5 ') (hereinafter also referred to as a "compound (5')" ) May be included. In the case of synthesizing a polyimide precursor in which the structural unit (56) is contained in the main chain (excluding the terminal) of the polyimide precursor, the compound (5) is preferably used, and the polyimide precursor In the case of synthesizing a polyimide precursor containing the unit (56), it is preferable to use the compound (5 ').

These compounds may be used singly or in combination of two or more.

'Of, A is A and agreement in the formula (5) and (6), R ¹² is the formula (6 Formula 5' is synonymous with R ¹² in).

When the total amount of the entire raw material compound (component (A) + component (B)) is 100 mass%, the compound (5) and / or compound The compounding amount of the compound (5) and the compound (5 ') is preferably from 0 to 15% by mass, more preferably from 0 to 10% by mass, and still more preferably from 0 to 5% by mass in view of obtaining a film, 9% by mass, and particularly preferably 0% by mass to 8% by mass. Preferably, the compounding amount of the compound (5) and the compound (5 ') is an amount when the compound (6) and / or the compound (6') is not used in synthesizing the polyimide precursor.

The polyimide precursor has a molar ratio (component (A) / component (B)) of the component (A) to the component (B) is 0.8 to 1.2 , More preferably in the range of 0.90 to 1.0. When the molar ratio of the component (A) to the component (B) is less than 0.8 equivalents or exceeds 1.2 equivalents, the molecular weight becomes small, making it difficult to form the polyimide film.

The reaction of the component (A) and the component (B) is usually carried out in an organic solvent. The organic solvent is preferably dehydrated.

As the organic solvent, it is preferable to use the following non-amide type solvent from the viewpoints of easiness of production of the resin composition of the present invention and properties (haze, warpage, etc.) of the obtained film.

As a specific method of reacting the component (A) and the component (B), at least one component (B) is dissolved in an organic solvent, at least one component (A) Deg.] C for 1 to 60 hours, and the like.

The total amount of the components (A) and (B) in the reaction liquid is preferably 3 to 60 mass%, more preferably 5 to 40 mass%, and still more preferably 10 to 40 mass% , And particularly preferably from 10 to 30 mass%.

When the total amount of the component (A) and the component (B) in the reaction liquid is in the above range, the resin composition having the polyimide precursor concentration in the resin composition obtained is preferably in the following preferable range.

When a solvent containing the following non-amide-based solvent as the organic solvent is used, it is preferable to use the composition containing the polyimide precursor and the organic solvent obtained in the above reaction as it is as the resin composition of the present invention. Can be obtained by isolating the polyimide precursor obtained in the above reaction as a solid component and then redissolving it in a solvent containing the following non-amide-based solvent as a main component.

As a method for isolating the polyimide precursor, a solution containing a polyimide precursor and an organic solvent is introduced into a poor solvent for a polyimide precursor such as methanol or isopropanol to precipitate the polyimide precursor or the like, A method of separating the polyimide precursor as a solid component, and the like.

Examples of the non-amide solvent used in the resin composition of the present invention include at least one organic solvent selected from the group consisting of an ether solvent, an ester solvent, a nitrile solvent, a sulfoxide solvent, and a ketone solvent.

Since the resin composition of the present invention contains a solvent containing the above-mentioned non-amide type solvent as a main component, the drying rate at the time of film formation is increased and the film quality is not deteriorated due to opacity. Further, by using a solvent containing the above-mentioned non-amide type solvent as a main component, a resin composition having a high concentration of the polyimide precursor can be obtained. The film having excellent productivity and having a good film quality can be obtained only by using a composition comprising the polyimide precursor and a solvent containing the biamide-based solvent as a main component.

In the present invention, the "solvent containing a non-amide type solvent as a main component" means a solvent containing a non-amide type solvent in an amount of preferably 70% by mass or more, more preferably 90% by mass or more, Refers to a solvent containing 95% by mass or more.

The ketone solvent is preferably a ketone having 3 to 10 carbon atoms and more preferably 3 to 6 carbon atoms in terms of boiling point and cost. Specific examples of preferred ketone solvents include acetone (boiling point = 57 ° C), methyl ethyl ketone (boiling point = 80 ° C), methyl-n-propyl ketone (boiling point = 105 ° C) Methyl-sec-butyl ketone (boiling point = 118 占 폚), diethyl ketone (boiling point = 101 占 폚), methyl n-butyl ketone Dialkyl ketones such as methyl-tert-butyl ketone (boiling point = 116 ° C), cyclopentanone (boiling point = 130 ° C), cyclohexanone (CHN, boiling point = 155 ° C), cycloheptanone , and? -butyrolactone (boiling point = 204 占 폚), and the like. Of these, cyclohexanone is preferable in that a resin composition excellent in dryness, productivity, and the like can be obtained.

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

The ether solvent is preferably an ether having 3 to 10 carbon atoms and more preferably an ether having 3 to 7 carbon atoms. Specific examples of the ether solvent include mono- or dialkyl ethers such as ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether and propylene glycol monoethyl ether (119 ° C), cyclic ethers such as dioxane and tetrahydrofuran , And anisole, and the like. Among them, propylene glycol monoethyl ether is preferable in view of obtaining a resin composition having good storage stability and a film having excellent transparency and mechanical strength.

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

The nitrile solvent is preferably a nitrile having 2 to 10 carbon atoms and more preferably a nitrile having 2 to 7 carbon atoms. Preferable nitrile solvents include acetonitrile (bp = 82 ° C), propanenitrile (bp = 97 ° C), butyronitrile (bp = 116 ° C), isobutyronitrile = 140 占 폚), isovaleronitrile (bp = 129 占 폚), and benzonitrile (bp = 191 占 폚). Of these, acetonitrile is preferable on the surface of a low boiling point or the like.

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

The ester solvent is preferably an ester having 3 to 10 carbon atoms and more preferably an ester having 3 to 6 carbon atoms. Preferred ester solvents include ethyl acetate (bp = 77 ° C), propyl acetate (bp = 97 ° C), acetic acid-i-propyl (bp = 89 ° C), butyl acetate (bp = 126 ° C), propylene glycol monoethyl acetate (bp = 146 占 폚); cyclic esters such as? -propiolactone (bp = 155 占 폚); and the like.

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

The sulfoxide-based solvent is preferably sulfoxides having 3 to 10 carbon atoms, and preferred examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like.

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

As the solvent containing the above-mentioned non-amide type solvent as a main component, at least one kind of organic solvent selected from the group consisting of a nitrile type solvent, an ether type solvent and a ketone type solvent is preferable, Ether-based solvents, and the like. These solvents have high solubility of the precursor having the structural unit (1), and by using these solvents, a resin composition having excellent storage stability can be obtained.

As the solvent containing the above-mentioned non-amide type solvent as a main component, it is preferable to use a mixed solvent of two or more kinds in combination, and in consideration of physical properties of the resultant film, a solvent mixed with a solvent whose boiling point is different by 20 ° C or more is preferable.

When the resin composition of the present invention contains the above mixed solvent, a resin composition having a high concentration of the polyimide precursor can be obtained.

As the mixed solvent, propylene glycol monoethyl ether (boiling point = 119 占 폚), butyl acetate (boiling point = 126 占 폚), and the like are preferably used in consideration of film properties such as film dryness and productivity, Cyclohexanone (boiling point = 155 占 폚), cycloheptanone (boiling point = 185 占 폚),? -Butyrolactone (boiling point = 204 占 폚), and dimethylsulfoxide (Boiling point = 189 DEG C) is preferable.

The mixed solvent preferably contains 5 to 95 parts by mass of the solvent having the highest boiling point in the mixed solvent, more preferably 20 to 95 parts by mass, relative to 100 parts by mass of the mixed solvent, and considering the physical properties of the obtained film More preferably 20 to 65 parts by mass. It is particularly preferable that the mixed solvent contains 20 to 55 parts by mass of the solvent having the highest boiling point in the mixed solvent with respect to 100 parts by mass of the mixed solvent. When the mixed solvent contains the solvent having the highest boiling point in this amount, A certain solvent remains even after drying at a temperature exceeding 120 캜, and the film can be fixed without film breakage. Thus, a resin composition having excellent productivity can be obtained, and film quality characteristics such as cloudiness and tensile strength and storage stability are excellent , It is possible to obtain a film which is excellent in adherence / peeling property to a substrate and is less prone to warping.

The resin composition of the present invention may also contain additives such as an antioxidant, an ultraviolet absorber and a surfactant within the range not impairing the object of the present invention.

The viscosity of the resin composition of the present invention depends on the molecular weight and concentration of the polyimide precursor, but is usually 500 to 50,000 mPa · s, preferably 500 to 20,000 mPa · s. When the viscosity of the resin composition is in the above range, the retention of the resin composition in the film is excellent and the film thickness can be easily adjusted, so that the film can be easily molded.

The viscosity of the resin composition was measured at 25 캜 in the atmosphere using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., Visel MODEL RE100).

The polyimide precursor concentration in the resin composition of the present invention is preferably adjusted so that the viscosity of the resin composition is in the above range, and is preferably 3 to 60 mass%, more preferably 5 to 20 mass% 40 mass%, more preferably 10 mass% to 40 mass%, and particularly preferably 10 mass% to 30 mass%. When the concentration of the polyimide precursor in the resin composition is within the above range, it is possible to form a thick film, a pinhole hardly occurs, and a film having excellent surface smoothness can be formed.

When the viscosity of the resin composition of the present invention and the polyimide precursor concentration in the composition are within the above ranges, the resin composition can be coated on the substrate using a slit coating method having excellent productivity and the like, It can be formed in a short time with good productivity.

&Lt; Film formation method &

The method for forming a film of the present invention includes a step of forming a coating film by applying the resin composition of the present invention onto a substrate, a step of evaporating a solvent containing the above-mentioned non-amide type solvent as a main component from the coating film, And a method comprising a step of heating.

Examples of a method for forming the coating film by applying the resin composition on a substrate include a roll coating method, a gravure coating method, a spin coating method, a slit coating method, a dipping method, a doctor blade, a dice, a coater, a spray, And then applying the coating solution. The thickness of the film, the surface smoothness and the like can also be controlled by repeating application. Of these, the slit coating method is preferable.

The thickness of the coating film is appropriately selected according to the intended use and is not particularly limited. For example, it is 1 to 500 탆, preferably 1 to 450 탆, more preferably 2 to 250 탆, Is 2 to 150 mu m, and particularly preferably 5 to 125 mu m.

Examples of the substrate include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a polybutylene terephthalate (PBT) film, a nylon 6 film, a nylon 6,6 film, a polypropylene film, a polytetrafluoroethylene A belt, a silicon wafer, a glass wafer, an oxide wafer, a glass substrate (including an alkali-free glass substrate), a Cu substrate, and an SUS plate. Particularly, since the resin composition of the present invention has excellent adhesion with the substrate and peelability, it is possible to form a thin film on a silicon wafer, a glass wafer, a glass substrate, a Cu substrate, an SUS plate and the like.

Specifically, the step of evaporating the solvent containing the non-amide-based solvent as the main component from the coating film can be carried out by vacuum drying or heating. However, considering transparency of the imidized film, It is preferable to evaporate the solvent. In consideration of productivity, it is preferable to perform only by heating without vacuum drying.

The heating conditions may be appropriately determined depending on the substrate and the polyimide precursor and the solvent to be used. For example, the heating temperature is preferably 60 ° C to 200 ° C, more preferably 90 to 180 ° C / RTI > The heating time is preferably 10 minutes to 1 hour. When the heating temperature is lower than 60 ° C, evaporation of a certain amount of solvent takes time, resulting in poor productivity. When the heating temperature exceeds 200 ° C, imidization proceeds before evaporation of the solvent, which may result in deterioration of film quality.

(Preferably a solvent having a boiling point of not lower than the heating temperature in the step of vaporizing the solvent containing the above-mentioned non-amide-based solvent as a main component from the coating film, more preferably a solvent having a boiling point of not less than 120 ° C Solvent, more preferably a solvent having a boiling point of 150 to 250 DEG C) is used, evaporation does not progress more than necessary in the step of evaporating the solvent, and therefore, a slight amount of solvent Point solvent) is considered to be included in the coating film. It is considered that the coating film contains a solvent having a high boiling point in the imidation step, thereby improving the strength of the film after the imidation step. Therefore, in the film forming method of the present invention, it is preferable to use a resin composition containing a mixed solvent containing a high boiling point solvent in order to obtain a film having excellent mechanical strength.

The step of imidizing the precursor can be performed by heating.

The heating may be carried out by evaporating the solvent to imidize the polyimide precursor. The polyimide precursor may be appropriately determined depending on the substrate or the polyimide precursor. For example, heating at a temperature of 200 to 450 ° C for 30 minutes to 2 hours desirable. More preferably 300 to 450 ° C for 30 minutes to 2 hours, more preferably 350 to 450 ° C for 30 minutes to 1 hour. It may also be heated under reduced pressure if necessary.

The heating atmosphere is not particularly limited, but is preferably in an atmosphere or in an inert gas atmosphere, and particularly preferably in an inert gas atmosphere. As the inert gas, nitrogen, argon, helium and the like can be mentioned from the standpoint of colorability, but nitrogen is preferable.

The heating may be performed by drying the coating film formed on the substrate for each substrate. However, after drying to some extent (for example, after the step of evaporating the solvent), the substrate The coating film formed on the substrate may be peeled from the substrate and then heated.

The film obtained through the above film forming process can be used by being peeled from the substrate, or can be used as it is without peeling off.

The thickness of the obtained film is appropriately selected according to the intended use, and is preferably 1 to 200 占 퐉, more preferably 5 to 100 占 퐉, still more preferably 10 to 50 占 퐉, particularly preferably 20 to 40 占 퐉.

The tensile strength of the film obtained from the resin composition of the present invention is 100 MPa or more, particularly preferably 200 MPa or more. If the elastic modulus of the film is less than 100 MPa, there is a case where the film is broken when peeling off the substrate from the substrate.

The glass transition temperature of the film is 250 DEG C or higher, preferably 350 DEG C or higher, particularly preferably 450 DEG C or higher. When the solder reflow process or device fabrication is performed, the film is heated to 250 DEG C or higher. If the glass transition temperature is less than 250 DEG C, the film may be deformed when the film is used for such a use.

Preferable uses of the film include an insulating film used for electronic parts such as a flexible printed substrate, a flexible substrate such as a flexible display substrate, a semiconductor element, a thin film transistor liquid crystal display element, a magnetic head element, an integrated circuit element, a solid- , Films for various capacitors, and the like. In these electronic parts, an interlayer insulating film, a planarizing insulating film, a surface protecting insulating film (an overcoating film, a passivation film, etc.) are provided in order to insulate the wirings arranged in a generally layered form, and they can be suitably used as these insulating films.

The film can be suitably used as a film of a light guide plate, a polarizing plate, a display film, an optical disk film, a transparent conductive film, a waveguide plate or the like.

Particularly, since the film is excellent in adhesion to a glass substrate and peelability, it is not necessary to provide an adhesive layer or the like between the film and the substrate, which may reduce the number of steps in manufacturing a flexible substrate.

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]

A three-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirring blade was charged with 153050 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB) 4.2925 g (0.000976 mol) of the amino-modified side chain phenylmethyl silicone X-22-1660B-3 (Shin-Etsu Chemical Co., Ltd.) at both ends, and the polyimide precursor 184.527 g of dehydrated cyclohexanone (CHN) was added so that the concentration became 14%, and the mixture was stirred for 10 minutes until a completely homogeneous solution was obtained. 10.3997 g (0.047679 mol) of pyromellitic dianhydride (PMDA) was added thereto, and the reaction was terminated by stirring for 60 minutes, followed by microfiltration using a polytetrafluoroethylene filter (pore size 1 μm) Whereby a resin composition 1 was prepared.

(Number of moles of PMDA / (number of moles of TFMB + number of moles of X-22-1660B-3) = 0.977 equivalent)

[Method of forming film after drying]

A glass substrate (length: 300 mm × length: 350 mm × thickness: 0.7 mm) was fixed to a control coater stand so as to be perpendicular to gravity, and the gap interval was set to 405 μm so that the film thickness after drying was 30 μm , And the resin composition 1 (12 g) was cast at the center of the glass substrate so as to be a coating film having a width of 200 mm and a length of 220 mm. Three sheets of glass substrates with coated films were produced.

Subsequently, the thus obtained coated glass substrate was dried by each of the following methods (1) to (3) to obtain a film after drying.

(1) The pressure was reduced to 0.1 mmHg after 10 minutes at 25 DEG C by a vacuum drier, then returned to the atmospheric pressure (760 mmHg), followed by heating and drying at 140 DEG C for 10 minutes

(2) Heat-dried on a hot plate at 155 ° C for 10 minutes

(3) Heat-dried on a hot plate at 170 ° C for 10 minutes

[Method of forming polyimide film]

A glass substrate (length: 300 mm × length: 350 mm × thickness: 0.7 mm) was fixed to a control coater stand provided so as to be perpendicular to gravity, and the gap interval was set to 405 μm , And the resin composition 1 (12 g) was cast at the center of the glass substrate so as to be a coating film having a width of 200 mm and a length of 220 mm.

Subsequently, the thus obtained coated glass substrate was put in a vacuum dryer, and after 10 minutes at 25 DEG C, the pressure was reduced to 0.1 mmHg, then returned to normal pressure (760 mmHg) and vacuum drying was completed. Thereafter, the glass substrate with a coated film after vacuum drying was heated and dried at 140 占 폚 for 10 minutes (primary drying), and then heated and dried (secondary drying) at 400 占 폚 for 30 minutes in a nitrogen atmosphere in a variable atmosphere drier, Of a polyimide film was obtained.

[Example 2]

2.0370 g of TFMB (12.6570 g) and 4,4'-diaminodiphenyl ether (ODA) were used in place of TFMB (15.3050 g), and the amounts of X-22-1660B-3, PMDA and CHN The resin composition 2 was obtained in the same manner as in Example 1 except that the composition was changed as shown.

A film was formed after drying in the same manner as in Example 1 except that the resin composition 2 was used instead of the resin composition 1.

A polyimide film was formed in the same manner as in Example 1 except that the resin composition 2 was used instead of the resin composition 1 and the secondary drying temperature was changed to 300 캜.

[Example 3]

Except that 147.622 g of CHN and 36.905 g of? -Butyrolactone were used instead of 184.527 g of CHN, and the amounts of TFMB, X-22-1660B-3 and PMDA were changed as shown in Table 1 To obtain a resin composition 3.

A film and a polyimide film were formed after drying in the same manner as in Example 2 except that the resin composition 3 was used instead of the resin composition 2.

[Example 4]

Except that 92.920 g of CHN and 92.264 g of? -Butyrolactone were used instead of 184.527 g of CHN, and the amounts of TFMB, X-22-1660B-3 and PMDA were changed as shown in Table 1 To obtain Resin Composition 4.

A film and a polyimide film were formed after drying in the same manner as in Example 2 except that the resin composition 4 was used instead of the resin composition 2.

[Example 5]

Except that 91.804 g of CHN and 91.804 g of? -Butyrolactone were used instead of 183.607 g of CHN and the amounts of TFMB, ODA, X-22-1660B-3 and PMDA were changed as shown in Table 1, To obtain a resin composition 5.

A film and a polyimide film were formed after drying in the same manner as in Example 2 except that the resin composition 5 was used instead of the resin composition 2.

[Example 6]

92.000 g of CHN and 92.000 g of dimethylsulfoxide were used instead of 184.527 g of CHN, and the amounts of TFMB, X-22-1660B-3 and PMDA were changed as shown in Table 1, To obtain a resin composition 6.

A film and a polyimide film were formed after drying in the same manner as in Example 2 except that the resin composition 6 was used instead of the resin composition 2.

[Example 7]

184.527 g of propylene glycol monoethyl ether was used instead of 184.527 g of CHN, and TFMB, X-22-1660B-3 and PMDA were used in the amounts shown in Table 1, to obtain Resin Composition 7.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 7 was used instead of the resin composition 1.

[Example 8]

Except that 92.2635 g of propylene glycol monoethyl ether and 92.2635 g of propylene glycol monoethyl ether acetate were used instead of 184.527 g of CHN and TFMB, X-22-1660B-3 and PMDA were used in the amounts shown in Table 1, The resin composition 8 was obtained in the same manner.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 8 was used instead of the resin composition 1.

[Example 9]

Except that 147.6216 g of propylene glycol monoethyl ether and 36.905 g of? -Butyrolactone were used instead of 184.527 g of CHN and TFMB, X-22-1660B-3 and PMDA were used in the amounts shown in Table 1 To obtain a resin composition 9.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 9 was used instead of the resin composition 1.

[Example 10]

73.8108 g of propylene glycol monoethyl ether, 73.8108 g of propylene glycol monoethyl ether acetate and 36.905 g of? -Butyrolactone were used instead of 184.527 g of CHN, and the amounts of TFMB, X-22-1660B-3 and PMDA , And the procedure of Example 1 was repeated to obtain Resin Composition 10.

A film and a polyimide film were formed after drying in the same manner as in Example 1 except that the resin composition 10 was used in place of the resin composition 1.

[Example 11]

138.3953 g of propylene glycol monoethyl ether and 46.1318 g of butyl acetate were used instead of 184.527 g of CHN, and TFMB, X-22-1660B-3 and PMDA were used in the amounts shown in Table 2, Composition 11 was obtained.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 11 was used in place of the resin composition 1.

[Example 12]

Except that 110.7162 g of propylene glycol monoethyl ether, 36.905 g of butyl acetate and 36.905 g of? -Butyrolactone were used instead of 184.527 g of CHN, and TFMB, X-22-1660B-3 and PMDA were used in the amounts shown in Table 2, The resin composition 12 was obtained in the same manner as in Example 1.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 12 was used instead of the resin composition 1.

[Example 13]

Using 92.2635 g of methyl isobutyl ketone, 46.132 g of CHN and 46.132 g of? -Butyrolactone, using TFMB, X-22-1660B-3 and PMDA in the amounts shown in Table 2 instead of 184.527 g of CHN, 1 to obtain Resin Composition 13.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 13 was used in place of the resin composition 1.

[Example 14]

Except that 110.7162 g of propylene glycol monoethyl ether, 36.905 g of butyl acetate and 36.905 g of? -Butyrolactone were used instead of 184.527 g of CHN, and TFMB, both terminal amino-modified dimethyl silicone KF-8012 (manufactured by Shin-Etsu Chemical Co., ) And PMDA were used in the amounts shown in Table 2, the procedure of Example 1 was repeated to obtain Resin Composition 14.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 14 was used instead of the resin composition 1.

[Example 15]

In the same manner as in Example 1, using 92.2635 g of methyl isobutyl ketone, 46.132 g of CHN and 46.132 g of? -Butyrolactone, using TFMB, KF-8012 and PMDA in the amounts shown in Table 2 instead of 184.527 g of CHN To obtain a resin composition 15.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 15 was used instead of the resin composition 1.

[Comparative Example 1]

Except that 12.2531 g of m-tolidine (mTB) was used instead of TFMB (15.3050 g), and the amounts of X-22-1660B-3, PMDA and CHN were changed as shown in Table 2. The resin composition 16 was obtained in the same manner.

The obtained resin composition 16 was used to form a film and a polyimide film after drying in the same manner as in Example 1, but the film and the film could not be formed.

[Comparative Example 2]

Except that 184.527 g of N-methylpyrrolidone was used instead of 184.527 g of CHN and the amount of TFMB, X-22-1660B-3 and PMDA used was changed as shown in Table 2 Thereby obtaining a resin composition 17.

A film and a polyimide film were formed after drying in the same manner as in Example 1, except that the resin composition 17 was used instead of the resin composition 1.

[Evaluation of properties of resin composition]

(1) Resin composition viscosity

The viscosity of the resin composition at 25 캜 was measured using 1.5 g of the resin composition obtained in Examples and Comparative Examples. Specifically, it was measured using a MODEL RE100 viscometer manufactured by Toki Sangyo Co., Ltd. The results are shown in Table 1 or 2.

(2) The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)

The weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the polyimide precursor in the resin compositions obtained in Examples and Comparative Examples were measured using a HLC-8220 type GPC apparatus (guard column: TSk guard colomn ALPHA column: TSKgelALPHA-M, developing solvent: NMP). The results are shown in Table 1 or 2.

(3) Storage stability at -15 캜

The resin compositions obtained in Examples and Comparative Examples were stored at -15 占 폚 for 48 hours. By visual observation, a sample which was transparent and had no precipitate was evaluated as "? &Quot;, and the sample in which opaque precipitates were precipitated was evaluated as " X ". The results are shown in Table 1 or 2.

[Evaluation of film after drying]

(4) Immobilization

The film after drying by the above methods (1) to (3) was rubbed strongly with a metal spatterer, and it was evaluated as " immobilization " The results are shown in Table 1 or 2.

(5) Whether there is cloudiness

The presence or absence of opacity of the film after drying by the methods (1) to (3) was visually confirmed. The results are shown in Table 1 or 2.

[Evaluation of polyimide film]

(6) Glass transition temperature (Tg)

The polyimide film obtained in Examples and Comparative Examples was peeled off from the glass substrate and the film after peeling was measured in the range of 40 to 450 占 폚 at a heating rate of 20 占 폚 / min under nitrogen using Thermo Plus DSC8230 manufactured by Rigaku . The results are shown in Table 1 or 2.

(7) Coefficient of linear expansion

The polyimide films obtained in Examples and Comparative Examples were peeled off from the glass substrate, and the peeled films were measured at a temperature raising rate of 6 캜 / min in a range of 25 to 350 캜 using Seiko Instrument SSC / 5200. From the measurement results, the coefficient of linear expansion at 100 to 200 ° C was calculated. The results are shown in Table 1 or 2.

(8) Film strength

Using the dumbbell No. 7 of JIS K6251, the polyimide film obtained in Examples and Comparative Examples was peeled off from the glass substrate, and a 30 占 퐉 film after peeling was subjected to a tensile test at 23 占 폚 at a speed of 50 mm / min to measure a tensile strength Were measured. The results are shown in Table 1 or 2.

(9) Peeling property with glass substrate

After the secondary drying, the 30 mu m polyimide film with the glass substrate was cut with a cutter so as to have a width of 10 mm and a length of 50 mm. The remaining film on the glass substrate was peeled to a length of 20 mm, A force of 50 mm / min was applied to measure the peel strength. The results are shown in Table 1 or 2.

(10) Transparency

The polyimide films obtained in Examples and Comparative Examples were peeled off from the glass substrate and the haze (haze) of the film after peeling was measured in accordance with the JIS K7105 transparency test method. Specifically, the measurement was carried out using an SC-3H type haze meter manufactured by Suga Shikikisha. The results are shown in Table 1 or 2.

(11) Deflection of film

A 30 占 퐉 polyimide film with a glass substrate obtained in the Examples and Comparative Examples was cut into a size of 60 mm 占 60 mm with a cutter, and the floating of the four ends was measured to calculate an average value. The results are shown in Table 1 or 2.

[Evaluation results]

The dried films obtained from the resin compositions 1 to 15 had a high drying speed and excellent adhesion to the glass substrate. In addition, a strong polyimide film having no warping, excellent in heat resistance at a Tg of 450 DEG C or higher, excellent in transparency, peelability from a glass substrate, and low in coefficient of linear expansion was obtained.

Since the polyimide precursor contained in the resin composition 16 did not have the structural unit (1), the resin composition obtained had a viscosity of 50,000 or more, cloudiness was observed, and a coating film could not be formed on the substrate. From the above results, it was found that if the polyimide precursor does not contain the structural unit (1), a resin composition having excellent productivity can not be obtained.

Since the resin composition 17 did not contain a non-amide-based solvent, cloudiness was observed immediately after the preparation of the composition, and storage stability remarkably deteriorated. From the above results, it was found that a resin composition having excellent storage stability could not be obtained without using a non-amide type solvent.

Claims

A resin composition comprising a polyimide precursor having a structural unit represented by the following formula (2) and having a structural unit represented by the following formula (1), and a solvent containing 70% by mass or more of a non-amide-based solvent.

(1), R represents independently a hydrogen atom or a monovalent organic group, R ¹ independently represents a group containing a group selected from the group represented by the following formula (3), R ² independently represents a tetravalent And n represents a positive integer, provided that at least one of R ¹ and R ² includes a halogen atom or a halogenated alkyl group)

The resin composition according to claim 1, wherein the solvent is a mixed solvent comprising two or more kinds of solvents.

The resin composition according to claim 2, wherein the solvent contains a solvent having the highest boiling point in the mixed solvent at 20 wt% or more based on 100 wt% of the total amount of the mixed solvent.

The resin composition according to claim 1, wherein the polyimide precursor has a weight average molecular weight of 10000 to 1000000.

The resin composition according to claim 1, wherein the concentration of the polyimide precursor in the resin composition is 3 to 60 mass%.

The resin composition according to claim 1, wherein the viscosity measured by an E-type viscometer (25 ° C) is in the range of 500 to 50000 mPa · s.

The resin composition according to claim 1, which is for forming a film.

A step of applying the resin composition according to claim 1 on a substrate to form a coating film;
A step of evaporating the solvent from the coating film,
A step of imidizing the polyimide precursor
&Lt; / RTI >

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