JP2022007960A - Polyimide precursor composition and polyimide film/substrate laminate - Google Patents

Abstract

To provide a polyimide precursor composition which enables production of a polyimide film/substrate laminate reduced in warpage and has excellent stability, and to provide a polyimide film/substrate laminate and a production method of a flexible electronic device.SOLUTION: A polyimide precursor composition comprises: a polyimide precursor having a spiro ring structure and benzene ring structures bound by an amide group; at least one imidazole compound contained in an amount ranging from more than 0.01 mole to less than 1 mole relative to 1 mole of repeating units of the polyimide precursor and selected from 2-phenylimidazole and benzimidazole; and a solvent.SELECTED DRAWING: Figure 1

Description

The present invention relates to a polyimide precursor composition preferably used for electronic device applications such as substrates for flexible devices and a polyimide film / substrate laminate with reduced warpage. In addition, the present invention relates to a method for manufacturing a flexible electronic device using the composition.

Polyimide films have been widely used in fields such as electrical / electronic device fields and semiconductor fields because they are excellent in heat resistance, chemical resistance, mechanical strength, electrical characteristics, dimensional stability, and the like. On the other hand, in recent years, with the advent of the advanced information society, the development of optical materials such as optical fibers and optical waveguides in the optical communication field, liquid crystal alignment films in the display device field, and protective films for color filters has been progressing. Especially in the field of display devices, a lightweight and highly flexible plastic substrate is being studied as an alternative to a glass substrate, and a display that can be bent or rolled is being actively developed.

In displays such as liquid crystal displays and organic EL displays, semiconductor elements such as TFTs for driving each pixel are formed. Therefore, the substrate is required to have heat resistance and dimensional stability. Polyimide film is promising as a substrate for display applications because it is excellent in heat resistance, chemical resistance, mechanical strength, electrical characteristics, dimensional stability, and the like.

Since polyimide is generally colored yellowish brown, its use in transmissive devices such as liquid crystal displays equipped with a backlight has been restricted, but in recent years, in addition to mechanical and thermal properties, it has been restricted. A polyimide film having excellent transparency has been developed, and expectations are further increasing as a substrate for display applications (see Patent Documents 1 to 3).

In general, it is difficult to maintain flatness of a flexible film, so it is difficult to uniformly and accurately form semiconductor elements such as TFTs, fine wiring, and the like on the flexible film. For example, Patent Document 4 describes, "a step of applying a specific precursor resin composition on a carrier substrate to form a solid polyimide resin film, a step of forming a circuit on the resin film, and the circuit. A method for manufacturing a flexible device, which is a display device or a light receiving device, including each step of peeling a solid resin film formed on the surface of the carrier substrate from the carrier substrate is described.

Further, in Patent Document 5, as a method for manufacturing a flexible device, elements and circuits necessary for the device are formed on a polyimide film / glass substrate laminate obtained by forming a polyimide film on a glass substrate. Later, a method including irradiating a laser from the glass substrate side to peel off the glass substrate is disclosed.

Patent Document 6 contains a polyimide precursor composition and an imidazole compound containing a repeating unit derived from a compound in which one of the tetracarboxylic acid component and the diamine component has an alicyclic structure and the other has an aromatic ring. It is disclosed that a polyimide precursor composition and a polyimide film / glass base material laminate are produced using the polyimide precursor composition. The polyimide film obtained by the invention of Patent Document 6 has a small retardation in the thickness direction, is excellent in mechanical properties, and is also excellent in transparency.

International Publication No. 2012/011590 International Publication No. 2013/179727 International Publication No. 2014/038715 Japanese Unexamined Patent Publication No. 2010-20729 International Publication No. 2018/221607 International Publication No. 2015/080158

When the methods of Patent Documents 4 and 5 are applied to actual production, the polyimide film / glass base material laminate is warped, which makes it difficult to form the device accurately and deteriorates the handleability. In some cases. In particular, when a large glass substrate is used, as a specific example, it is applied to a so-called multi-chamfering method for manufacturing a large flexible electronic device (for example, a large display device) or a plurality of flexible electronic devices (for example, a display device) from one substrate. In this case, the warp may expand to a non-negligible extent.

According to the invention of Patent Document 6, a polyimide film having excellent properties can be obtained as described above, but the problem of warpage of the polyimide film / glass substrate laminate, the problem of stability of the polyimide precursor composition, and the problems thereof can be solved. There is no disclosure of the composition to be resolved.

The present invention has been made in view of the conventional problems, and a main object thereof is a polyimide precursor composition capable of producing a polyimide film / base material laminate having a small warp and having excellent stability. To provide things. Further, an object of one aspect of the present invention is to provide a polyimide film obtained by using the polyimide precursor composition and a polyimide film / base material laminate, and further, an object of another aspect of the present invention is. , A method for manufacturing a flexible electronic device using the polyimide precursor composition, and a flexible electronic device.

The main disclosure items of this application are summarized below.

1. 1. A polyimide precursor represented by the following general formula (I),
At least one imidazole compound and a solvent contained in an amount in the range of more than 0.01 mol to less than 1 mol and selected from 2-phenylimidazole and benzimidazole with respect to 1 mol of the repeating unit of the polyimide precursor. A polyimide precursor composition comprising.

（一般式Ｉ中、Ｘ_１は４価の脂肪族基または芳香族基であり、Ｙ_１は２価の脂肪族基または芳香族基であり、Ｒ_１およびＲ_２は互いに独立して、水素原子、炭素数１～６のアルキル基または炭素数３～９のアルキルシリル基であり、但し、Ｘ_１の７０モル％以上が、式（１－１）：

(In the general formula I, X ₁ is a tetravalent aliphatic group or an aromatic group, Y ₁ is a divalent aliphatic group or an aromatic group, and R ₁ and R ₂ are independent of each other and hydrogen. An atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, wherein 70 mol% or more of X ₁ is the formula (1-1) :.

で表される構造であり、Ｙ_１の６０モル％以上好ましくは１００モル％未満、特定の態様では７０モル％以上好ましくは１００モル％未満が、式（Ｄ－１）および／または（Ｄ－２）：

The structure represented by the formula (D-1) and / or (D-1) and / or (D-1) is 60 mol% or more and preferably less than 100 mol% of Y ₁ , and 70 mol% or more and preferably less than 100 mol% in a specific embodiment. 2):

で表される構造である。）

It is a structure represented by. )

In a preferred embodiment of item 1 above, the proportion of structures of formula (D- ₁ ) and / or (D-2) in Y1 is less than 100 mol%.

（式中、ｍは０～３を表し、ｎ１およびｎ２はそれぞれ独立に０～４の整数を表し、Ｂ_１およびＢ_２はそれぞれ独立に、炭素数１～６のアルキル基、ハロゲン基または炭素数１～６のフルオロアルキル基よりなる群から選択される１種を表し、Ｘはそれぞれ独立に、直接結合、または式：－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－で表される基よりなる群から選択される１種を表す。但し、前記式（Ｄ－１）および（Ｄ－２）は除く。）
で表される構造である。 In the preferred embodiment of the above item ₁ , the formula (G- ₁ ):

(In the formula, m represents 0 to 3, n1 and n2 each independently represent an integer of 0 to 4, and B ₁ and B ₂ independently represent an alkyl group, a halogen group or a carbon having 1 to 6 carbon atoms. Represents one selected from the group consisting of fluoroalkyl groups of numbers 1-6, where X is independently, directly bonded, or represented by the formulas: -NHCO-, -CONH-, -COO-, -OCO-. Represents one selected from the group consisting of groups, except for the formulas (D-1) and (D-2).
It is a structure represented by.

In a preferred embodiment of item 1 above, more than 0 mol% and 40 mol% or less of Y ₁ and, in a particular embodiment, more than 0 mol% and less than 30 mol% of Y ₁ , formula (B-1) and / or (B-). 2):

で表される構造である。
２． このポリイミド前駆体組成物から得られるポリイミドフィルムが、厚さ１０μｍのフィルムでの波長４００ｎｍの光透過率が７５％以上であることを特徴とする上記項１に記載のポリイミド前駆体組成物。

It is a structure represented by.
2. 2. Item 2. The polyimide precursor composition according to Item 1, wherein the polyimide film obtained from this polyimide precursor composition has a light transmittance of 75% or more at a wavelength of 400 nm in a film having a thickness of 10 μm.

3. 3. Item 2. The polyimide precursor composition according to Item 1 or 2, wherein the polyimide film obtained from this polyimide precursor composition has a breaking elongation of a film having a thickness of 10 μm of 10% or more.

4. The polyimide precursor composition according to any one of Items 1 to 3, wherein 90 mol% or more of X ₁ has a structure represented by the above formula (1-1).

5. The polyimide precursor composition is applied onto a silicon wafer to imidize it to produce a polyimide film / silicon wafer laminate having a thickness of 10 μm, and the polyimide film / silicon wafer laminate is used at 80 ° C. or higher, a glass transition temperature, and a glass transition temperature. Item 1 to above, which gives a polyimide film in which the residual stress at 23 ° C. is less than 27 MPa when the residual stress between the polyimide film and the silicon wafer obtained at a plurality of temperatures in the range of less than the lower decomposition temperature is linearly approximated. 4. The polyimide precursor composition according to any one of 4.
The plurality of temperatures for measuring the residual stress can be, for example, 150 ° C, 140 ° C, 130 ° C, 120 ° C and 110 ° C.

6. A polyimide film obtained from the polyimide precursor composition according to any one of Items 1 to 5 above.

7. A polyimide film obtained from the polyimide precursor composition according to any one of Items 1 to 5 above, and a polyimide film.
A polyimide film / base material laminate characterized by having a base material.

8. Item 2. The laminate according to Item 7, wherein the base material is a glass substrate.

9. (A) The step of applying the polyimide precursor composition according to any one of the above items 1 to 5 onto a base material, and (b) the polyimide precursor being heat-treated on the base material to obtain the above-mentioned A method for producing a polyimide film / substrate laminate, which comprises a step of laminating a polyimide film on a substrate.

10. Item 9. The manufacturing method according to Item 9, wherein the base material is a glass substrate.

11. (A) A step of applying the polyimide precursor composition according to any one of Items 1 to 5 above onto a substrate.
(B) A step of heat-treating the polyimide precursor on the base material to produce a polyimide film / base material laminate in which the polyimide film is laminated on the base material.
(C) Flexible electrons having a step of forming at least one layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminated body, and (d) a step of peeling the base material and the polyimide film. How to make the device.

12. Item 12. The manufacturing method according to Item 11, wherein the base material is a glass substrate.

13. (1) A step of preparing a polyimide film / reference base material laminate in which a polyimide film is formed on a reference base material.
(2) A step of measuring the radius of curvature of the polyimide film / reference base material laminate at a plurality of measurement temperatures of 80 ° C. or higher.
(3) A step of calculating the residual stress at the measured temperature between the polyimide film and the reference base material in the polyimide film / reference base material laminate based on the measured radius of curvature, and (4) a plurality of measurement temperatures. A method for evaluating residual stress of a polyimide film / base material laminate, which comprises a step of obtaining residual stress at a predetermined temperature based on the residual stress in.

14. Item 3. The method for evaluating residual stress according to Item 13, wherein the reference base material is a silicon substrate.

15. Item 3. The residual stress according to Item 13 or 14, further comprising a step of estimating warpage of the polyimide film / target substrate laminate at a predetermined temperature based on the residual stress of the polyimide film / reference substrate laminate at a predetermined temperature. Evaluation methods.

16. Item 5. The method for evaluating residual stress according to Item 15, wherein the target substrate is a glass substrate.

According to the present invention, it is possible to produce a polyimide film / base material laminate having a small warp, and it is possible to provide a polyimide precursor composition having excellent stability. According to the embodiment of the polyimide precursor composition of the present invention, in addition to the effect that (i) a polyimide film / glass substrate laminate having a small warp can be produced, (ii) the obtained polyimide film can be obtained. It has one or more of the effects of excellent transparency, (iii) the obtained polyimide film has excellent mechanical properties such as elongation at break, and (iv) excellent storage stability, and in a preferred embodiment (i). ), In addition to the effects of (ii) to (iv).

Further, according to one aspect of the present invention, it is possible to provide a polyimide film obtained by using the polyimide precursor composition and a polyimide film / base material laminate. Further, according to another aspect of the present invention, it is possible to provide a method for manufacturing a flexible electronic device using the polyimide precursor composition and a flexible electronic device.

It is a figure which shows typically the warp of the polyimide film / base material laminate. It is a figure for demonstrating the method of obtaining the residual stress of a polyimide film / reference base material laminate.

In the present application, the "flexible (electronic) device" means that the device itself is flexible, and a semiconductor layer (transistor, diode, etc. as an element) is usually formed on a substrate to complete the device. A "flexible (electronic) device" is distinguished from a device such as a COF (Chip On Film) in which a "hard" semiconductor element such as an IC chip is mounted on a conventional FPC (flexible printed wiring board). However, in order to operate or control the "flexible (electronic) device" of the present application, a "hard" semiconductor element such as an IC chip may be mounted on a flexible substrate or electrically connected to be fused and used. There is nothing wrong with doing it. Flexible (electronic) devices that are preferably used include liquid crystal displays, organic EL displays, display devices such as electronic paper, solar cells, and light receiving devices such as CMOS.

Hereinafter, the polyimide precursor composition of the present invention will be described, and then a method for manufacturing a flexible electronic device will be described.

<< Polyimide precursor composition >>
The polyimide precursor composition for forming the polyimide film contains a polyimide precursor, an imidazole compound and a solvent. Both the polyimide precursor and the imidazole compound are dissolved in the solvent.

The polyimide precursor has the following general formula (I):

（一般式Ｉ中、Ｘ_１は４価の脂肪族基または芳香族基であり、Ｙ_１は２価の脂肪族基または芳香族基であり、Ｒ_１およびＲ_２は互いに独立して、水素原子、炭素数１～６のアルキル基または炭素数３～９のアルキルシリル基である。）
で表される繰り返し単位を有する。特に好ましくは、Ｒ_１およびＲ_２が水素原子であるポリアミック酸である。Ｘ_１およびＹ_１が脂肪族基である場合、脂肪族基は好ましくは脂環構造を有する基である。

(In the general formula I, X ₁ is a tetravalent aliphatic group or an aromatic group, Y ₁ is a divalent aliphatic group or an aromatic group, and R ₁ and R ₂ are independent of each other and hydrogen. An atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms.)
It has a repeating unit represented by. Particularly preferred is a polyamic acid in which R ₁ and R ₂ are hydrogen atoms. When X ₁ and Y ₁ are aliphatic groups, the aliphatic group is preferably a group having an alicyclic structure.

Of all the repeating units in the polyimide precursor, X ₁ preferably contains 70 mol% or more of the structure represented by the following formula (1-1), that is, norbornane-2-spiro-α-cyclopentanone-α'. -Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid dianhydride (hereinafter, abbreviated as CpODA if necessary).

Among all the repeating units in the polyimide precursor, Y1 is 60 mol% or more, preferably less than ₁₀₀ mol%, and in a specific embodiment, preferably 70 mol% or more, preferably less than 100 mol%, according to the following formula (D-1). ) And / or the structure represented by (D-2), that is, a structure derived from 4,4'-diaminobenzanilide (abbreviated as DABAN if necessary).

By using a composition containing such a polyimide precursor, in addition to the effect of producing a polyimide film / glass substrate laminate having a small warp, by using an appropriate imidazole compound, transparency and breakage can be achieved. It is possible to manufacture a polyimide film having excellent mechanical properties such as elongation.

The polyimide precursor will be described by the monomers giving X ₁ and Y ₁ in the general formula (I) (tetracarboxylic acid component, diamine component, and other components), and then the production method will be described.

In the present specification, the tetracarboxylic acid component is tetracarboxylic acid, tetracarboxylic acid dianhydride, other tetracarboxylic acid silyl ester, tetracarboxylic acid ester, tetracarboxylic acid chloride and the like used as raw materials for producing polyimide. Contains carboxylic acid derivatives. Although not particularly limited, it is convenient to use tetracarboxylic dianhydride in production, and the following description describes an example in which tetracarboxylic dianhydride is used as the tetracarboxylic dianhydride component. The diamine component is a diamine compound having two amino groups (-NH ₂ ), which is used as a raw material for producing polyimide.

Further, in the present specification, the polyimide film means both a film formed on a (carrier) substrate and existing in the laminate, and a film after the substrate is peeled off. Further, the material constituting the polyimide film, that is, the material obtained by heat-treating (imidizing) the polyimide precursor composition may be referred to as "polyimide material".

<X ₁ and tetracarboxylic acid component>
As described above, in all the repeating units in the polyimide precursor, X ₁ preferably has a structure represented by the formula (1-1) in an amount of 70 mol% or more, more preferably 80 mol% or more, still more preferably. The structure represented by the formula (1-1) is 90 mol% or more, most preferably 95 mol% or more (100 mol% is also very preferable). The tetracarboxylic dianhydride that gives the structure of formula (1-1) as X ₁ is CpODA.

CpODA may be a mixture of stereoisomers or one particular stereoisomer. Although not particularly limited, preferred stereoisomers include trans-endo-endo-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-. Tetracarboxylic acid dianhydride (CpODA-tee) and cis-endo-endo-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 "-norbornane-5,5", 6,6 "- Examples thereof include tetracarboxylic acid dianhydride (CpODA-cee).

In one preferred embodiment, at least 50 mol% or more, even more preferably 63 mol% or more of CpODA is CpODA-tee. In one preferred different embodiment, at least 30 mol% or more, and even more preferably 37 mol% or more, of CpODA is CpODA-cee. In one preferred further different embodiment, the total of CpODA-tee and CpODA-cee in CpODA is at least 80 mol% or more, and even more preferably 83 mol% or more.

In the present invention, as X ₁ , a tetravalent aliphatic group or aromatic group (abbreviated as “other X ₁ ”) other than the structure represented by the formula (1-1) does not impair the effect of the present invention. It can be contained in a range of amounts. That is, the tetracarboxylic acid component can contain other tetracarboxylic acid derivatives in addition to CpODA in an amount within a range that does not impair the effects of the present invention. The amount of the other tetracarboxylic acid derivative is less than 30 mol%, more preferably less than 20 mol%, still more preferably less than 10 mol% (preferably 0 mol%) with respect to 100 mol% of the tetracarboxylic acid component. be.

When "other X ₁ " is a tetravalent group having an aromatic ring, a tetravalent group having an aromatic ring having 6 to 40 carbon atoms is preferable.

Examples of the tetravalent group having an aromatic ring include the following.

（式中、Ｚ_１は直接結合、または、下記の２価の基：

(In the formula, Z ₁ is directly bonded, or the following divalent group:

のいずれかである。ただし、式中のＺ_２は、２価の有機基、Ｚ_３、Ｚ_４はでそれぞれ独立にアミド結合、エステル結合、カルボニル結合であり、Ｚ_５は芳香環を含む有機基である。）

Is one of. However, Z ₂ in the formula is a divalent organic group, Z _{3 and} Z ₄ are independently amide bonds, ester bonds and carbonyl bonds, respectively, and Z ₅ is an organic group containing an aromatic ring. )

Specific examples of Z ₂ include an aliphatic hydrocarbon group having 2 to 24 carbon atoms and an aromatic hydrocarbon group having 6 to 24 carbon atoms.

Specific examples of Z ₅ include aromatic hydrocarbon groups having 6 to 24 carbon atoms.

As the tetravalent group having an aromatic ring, the following is particularly preferable because it can achieve both high heat resistance and high transparency of the obtained polyimide film.

（式中、Ｚ_１は直接結合、または、へキサフルオロイソプロピリデン結合である。）

(In the formula, Z ₁ is a direct bond or a hexafluoroisopropylidene bond.)

Here, since it is possible to achieve both high heat resistance, high transparency, and a low coefficient of linear thermal expansion of the obtained polyimide film, it is more preferable that Z ₁ is a direct bond.

In addition, as a preferable group, in the above formula (9), Z ₁ is the following formula (3A):

で表されるフルオレニル含有基である化合物が挙げられる。Ｚ_１１およびＺ_１２はそれぞれ独立に、好ましくは同一で、単結合または２価の有機基である。Ｚ_１１およびＺ_１２としては、芳香環を含む有機基が好ましく、例えば式（３Ａ１）：

Examples thereof include a compound which is a fluorenyl-containing group represented by. Z ₁₁ and Z ₁₂ are independent, preferably identical, single-bonded or divalent organic groups, respectively. As Z ₁₁ and Z ₁₂ , organic groups containing an aromatic ring are preferable, and for example, the formula (3A1)::

（Ｚ_１３およびＺ_１４は、互いに独立に単結合、－ＣＯＯ－、－ＯＣＯ－または－Ｏ－であり、ここでＺ_１４がフルオレニル基に結合した場合、Ｚ_１３が－ＣＯＯ－、－ＯＣＯ－または－Ｏ－でＺ_１４が単結合の構造が好ましく；Ｒ_９１は炭素数１～４のアルキル基またはフェニル基であり、好ましくはメチルであり、ｎは０～４の整数であり、好ましくは１である。）
で表される構造が好ましい。

(Z ₁₃ and Z ₁₄ are single bonds independently of each other, -COO-, -OCO- or -O-, where if Z ₁₄ is attached to a fluorenyl group, then Z ₁₃ is -COO-, -OCO-. Alternatively, a structure in which Z ₁₄ is a single bond in —O— is preferable; R ₉₁ is an alkyl group or a phenyl group having 1 to 4 carbon atoms, preferably methyl, and n is an integer of 0 to 4, preferably. 1)
The structure represented by is preferable.

Examples of the tetracarboxylic acid component that gives the repeating unit of the general formula (I) in which X ₁ is a tetravalent group having an aromatic ring include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane. , 4- (2,5-dioxotetratetra-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3', 4,4'-benzophenone Tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis (3,4-dicarboxy) Phenyl) sulfone, m-terphenyl-3,4,3', 4'-tetracarboxylic acid, p-terphenyl-3,4,3', 4'-tetracarboxylic acid, biscarboxyphenyldimethylsilane, bisdi Examples thereof include carboxyphenoxydiphenyl sulfide, sulfonyldiphthalic acid, and derivatives such as tetracarboxylic acid dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride. Examples of the tetracarboxylic acid component that gives the repeating unit of the general formula (I) in which X ₁ is a tetravalent group having an aromatic ring containing a fluorine atom include 2,2-bis (3,4-dicarboxy). Examples thereof include phenyl) hexafluoropropane and derivatives thereof such as tetracarboxylic acid dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester and tetracarboxylic acid chloride. Further, as a preferable compound, (9H-fluorene-9,9-diyl) bis (2-methyl-4,1-phenylene) bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) Can be mentioned. The tetracarboxylic acid component may be used alone or in combination of two or more.

When the "other X ₁ " is a tetravalent group having an alicyclic structure, a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms is preferable, and at least one aliphatic 4- to 12-membered ring, It is more preferable to have an aliphatic 4-membered ring or an aliphatic 6-membered ring. Tetravalent groups having a preferred aliphatic 4-membered ring or aliphatic 6-membered ring include:

（式中、Ｒ_３１～Ｒ_３８は、それぞれ独立に直接結合、または、２価の有機基である。Ｒ_４１～Ｒ_４７、およびＲ_７１～Ｒ_７３は、それぞれ独立に式：－ＣＨ_２－、－ＣＨ＝ＣＨ－、－ＣＨ_２ＣＨ_２－、－Ｏ－、－Ｓ－で表される基よりなる群から選択される１種を示す。Ｒ_４８は芳香環もしくは脂環構造を含む有機基である。）

(In the formula, R ₃₁ to R ₃₈ are independently directly bonded or divalent organic groups. R ₄₁ to R ₄₇ and R ₇₁ to R ₇₃ are independently formulas: -CH _2-- , respectively. , -CH = CH-, -CH ₂ CH _2- , -O-, -S- represents one selected from the group consisting of groups. R ₄₈ is an organic containing an aromatic ring or an alicyclic structure. Is the basis.)

Specific examples of the R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , and R ₃₈ include a direct bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples thereof include an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl bond, an ester bond, and an amide bond.

Examples of the organic group containing an aromatic ring as R ₄₈ include the following.

（式中、Ｗ_１は直接結合、または、２価の有機基であり、ｎ_１１～ｎ_１３は、それぞれ独立に０～４の整数を表し、Ｒ_５１、Ｒ_５２、Ｒ_５３は、それぞれ独立に炭素数１～６のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基である。）

(In the formula, W ₁ is a direct bond or a divalent organic group, n ₁₁ to n ₁₃ each independently represent an integer of 0 to 4, and R ₅₁ , R ₅₂ , and R ₅₃ are independent of each other. It is an alkyl group, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group having 1 to 6 carbon atoms.

Specific examples of W ₁ include a direct coupling, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).

（式（６）中のＲ_６１～Ｒ_６８は、それぞれ独立に直接結合または前記式（５）で表される２価の基のいずれかを表す。）

(R ₆₁ to R ₆₈ in the formula (6) represent either a direct coupling independently or a divalent group represented by the formula (5).)

As the tetravalent group having an alicyclic structure, the following ones are particularly preferable because they can achieve both high heat resistance, high transparency, and a low coefficient of linear thermal expansion of the obtained polyimide.

Examples of the tetracarboxylic acid component that gives the repeating unit of the formula (I) in which X ₁ is a tetravalent group having an alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic acid and isopropyridenediphenoxybis. Phthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-3,3', 4,4'-tetracarboxylic acid, [1,1'-bi (Cyclohexane)]-2,3,3', 4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,2', 3,3'-tetracarboxylic acid, 4,4'- Methylenebis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-oxybis (cyclohexane-1,2) -Dicarboxylic acid), 4,4'-thiobis (cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfonylbis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(dimethylsilanediyl) Bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl) Bis (cyclohexane-1,2-dicarboxylic acid), octahydropentalene-1,3,4 , 6-Tetracarboxylic acid, Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2,3,5 -Tricarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octa-5-ene-2,3,7,8-tetracarboxylic acid Acid, tricyclo [4.2.2.02,5] decane-3,4,7,8-tetracarboxylic acid, tricyclo [4.2.2.02,5] deca-7-en-3,4 9,10-Tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid Acid, decahydro-1,4-ethano-5,8-methanonaphthalene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4: 5,8: 9,10-trimethanoanthracen-2 , 3,6,7-Tetraca Examples thereof include rubon acid and derivatives such as tetracarboxylic acid dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester and tetracarboxylic acid chloride. The tetracarboxylic acid component may be used alone or in combination of two or more.

< _Y1 and diamine component>
As described above, in all the repeating units in the polyimide precursor, Y1 preferably has a structure represented by the formulas (D- ₁ ) and / or (D-2) in an amount of 60 mol% or more and preferably less than 100 mol%. There, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more are the structures represented by the formulas (D-1) and / or (D-2). The diamine compound giving the structure of the formula (D-1) and the formula (D-2) as Y ₁ is 4,4'-diaminobenzanilide (abbreviation: DABAN).

In the present invention, as Y ₁ , a divalent aliphatic group or aromatic group (abbreviated as “other Y ₁ ”) other than the structures represented by the formulas (D-1) and (D-2) is referred to as the present invention. It can be contained in an amount within a range that does not impair the effects of the invention. That is, the diamine component can contain other diamine compounds in addition to DABAN in an amount within a range that does not impair the effects of the present invention. The amount of the other diamine compound is preferably more than 0 mol% and 40 mol% or less, preferably 30 mol% or less (preferably less than 30 mol%), and more preferably 20 mol% or less with respect to 100 mol% of the diamine component. (Preferably less than 20 mol%), even more preferably 10 mol% or less (preferably less than 10 mol%).

（式中、ｍは０～３を表し、ｎ１およびｎ２はそれぞれ独立に０～４の整数を表し、Ｂ_１およびＢ_２はそれぞれ独立に、炭素数１～６のアルキル基、ハロゲン基または炭素数１～６のフルオロアルキル基よりなる群から選択される１種を表し、Ｘはそれぞれ独立に、直接結合、または式：－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－で表される基よりなる群から選択される１種を表す。但し、前記式（Ｄ－１）および（Ｄ－２）は除く。）
で表される構造を含むことが好ましい。 In a preferred embodiment of the invention, the proportion of structures of formula (D- ₁ ) and / or (D-2) in Y1 is less than 100 mol%. In this case, the other Y ₁ is the equation (G-1) :.

(In the formula, m represents 0 to 3, n1 and n2 each independently represent an integer of 0 to 4, and B ₁ and B ₂ independently represent an alkyl group, a halogen group or a carbon having 1 to 6 carbon atoms. Represents one selected from the group consisting of fluoroalkyl groups of numbers 1-6, where X is independently, directly bonded, or represented by the formulas: -NHCO-, -CONH-, -COO-, -OCO-. Represents one selected from the group consisting of groups, except for the formulas (D-1) and (D-2).
It is preferable to include the structure represented by.

m is preferably 0, 1 or ₂ , n1 and n2 are preferably 0 or ₁ , and B1 and B2 are preferably methyl or trifluoromethyl groups. For example, m = 0 with a structure of n1 = 0, m = 1 with a direct bond or -COO-, -OCO- with n1 = n2 = 0 or 1 structure, m = 2 with a direct bond or-. Examples include COO- and -OCO- structures. A particularly preferred structure is one in which m = 1 and X is a direct coupling.

The structure of the formula (G-1) is preferably more than 0 mol% and 40 mol% or less of Y ₁ , more preferably more than 0 mol% and 30 mol% or less of Y ₁ , and further preferably more than 5 mol% and 30 mol% or less. It is included in the ratio of. By including the structure of the formula (G-1), it is possible to improve mechanical properties such as breaking strength and optical properties while maintaining the effect that a polyimide film / glass substrate laminate having a small warp can be manufactured. can.

で表される構造を含む。 Particularly preferably, the other Y1 is the formula (B- ₁ ) and / or (B-2) :.

Includes the structure represented by.

Further, among the formulas (B-1) and (B-2), the formula (B-2) is more preferable. Further, as Y ₁ , "other Y ₁ " other than the formula (D-1), the formula (D-2) and the formula (G-1) is contained in a proportion of 10 mol% or less, more preferably 5 mol% or less. You may. Further, "other Y ₁ " other than the formula (D-1), the formula (D-2) and the formula (G-1) is 0 mol%, that is, Y ₁ is the formula (D-1). It is also very preferable that it consists only of the structures of the formula (D-2) and the formula (G-1).

When the "other Y ₁ " other than the formula (G-1) is a divalent group having an aromatic ring, it has an aromatic ring having 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms. A divalent group is preferred.

Examples of the divalent group having an aromatic ring include the following. However, as the "other Y ₁ " further included, those included in the formula (D-1), the formula (D-2) and the formula (G-1) are excluded.

（式中、Ｗ_１は直接結合、または、２価の有機基であり、ｎ_１１～ｎ_１３は、それぞれ独立に０～４の整数を表し、Ｒ_５１、Ｒ_５２、Ｒ_５３は、それぞれ独立に炭素数１～６のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基である。）

(In the formula, W ₁ is a direct bond or a divalent organic group, n ₁₁ to n ₁₃ each independently represent an integer of 0 to 4, and R ₅₁ , R ₅₂ , and R ₅₃ are independent of each other. It is an alkyl group, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group having 1 to 6 carbon atoms.

Specific examples of W ₁ include a direct coupling, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).

（式（６）中のＲ_６１～Ｒ_６８は、それぞれ独立に直接結合または前記式（５）で表される２価の基のいずれかを表す。）

(R ₆₁ to R ₆₈ in the formula (6) represent either a direct coupling independently or a divalent group represented by the formula (5).)

Here, since the high heat resistance, high transparency, and low coefficient of linear thermal expansion of the obtained polyimide can be compatible with each other, W ₁ can be directly bonded, or the formulas: -NHCO-, -CONH-, -COO-, -OCO-. It is particularly preferable that it is one selected from the group consisting of the groups represented by. Further, W ₁ is one selected from the group consisting of groups in which R ₆₁ to R ₆₈ are directly bonded or represented by the formulas: -NHCO-, -CONH-, -COO-, -OCO-. It is also particularly preferable that it is one of the divalent groups represented by the formula (6). However, when -NHCO- or _-CONH- is selected, "other Y1" is selected so as to be different from the formula (D-1) or the formula (D-2).

In addition, as a preferable group, in the above formula (4), W ₁ is the following formula (3B):

で表されるフルオレニル含有基である化合物が挙げられる。Ｚ_１１およびＺ_１２はそれぞれ独立に、好ましくは同一で、単結合または２価の有機基である。Ｚ_１１およびＺ_１２としては、芳香環を含む有機基が好ましく、例えば式（３Ｂ１）：

Examples thereof include a compound which is a fluorenyl-containing group represented by. Z ₁₁ and Z ₁₂ are independent, preferably identical, single-bonded or divalent organic groups, respectively. As Z ₁₁ and Z ₁₂ , organic groups containing an aromatic ring are preferable, and for example, the formula (3B1)::

（Ｚ_１３およびＺ_１４は、互いに独立に単結合、－ＣＯＯ－、－ＯＣＯ－または－Ｏ－であり、ここでＺ_１４がフルオレニル基に結合した場合、Ｚ_１３が－ＣＯＯ－、－ＯＣＯ－または－Ｏ－でＺ_１４が単結合の構造が好ましく；Ｒ_９１は炭素数１～４のアルキル基またはフェニル基であり、好ましくはフェニルであり、ｎは０～４の整数であり、好ましくは１である。）
で表される構造が好ましい。

(Z ₁₃ and Z ₁₄ are single bonds independently of each other, -COO-, -OCO- or -O-, where if Z ₁₄ is attached to a fluorenyl group, then Z ₁₃ is -COO-, -OCO-. Alternatively, a structure in which Z ₁₄ is a single bond in —O— is preferable; R ₉₁ is an alkyl group or a phenyl group having 1 to 4 carbon atoms, preferably phenyl, and n is an integer of 0 to 4, preferably. It is 1.)
The structure represented by is preferable.

As another preferable group, in the above formula (4), a compound in which W ₁ is a phenylene group, that is, a terphenyldiamine compound can be mentioned, and a compound having all parabonds is particularly preferable.

Another preferred group is a compound in which W ₁ is the first phenyl ring of the formula (6) and R ₆₁ and R ₆₂ are 2,2-propyridene groups in the above formula (4).

As yet another preferable group, in the above formula (4), W ₁ is the following formula (3B2):

で表される化合物が挙げられる。

Examples thereof include compounds represented by.

Examples of the diamine component that gives the repeating unit of the general formula (I) in which Y ₁ is a divalent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-. Biphenyl, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, m-tridin, 3,4'-diaminobenzanilide, N, N'-bis (4- Aminophenyl) terephthalamide, N, N'-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid Bis (4-aminophenyl) ester, p-phenylene bis (p-aminobenzoate), bis (4-aminophenyl)-[1,1'-biphenyl] -4,4'-dicarboxylate, [1,1 '-Biphenyl] -4,4'-diylbis (4-aminobenzoate), 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, p-methylenebis (phenylene) Diamine), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4) -Aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, bis (4-aminophenyl) sulfone, 3,3'-bis (trifluoromethyl) benzidine, 3,3'-bis ((aminophenoxy) phenyl) propane, 2,2'-bis (3) -Amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, octafluorobenzidine, 3,3'-dimethoxy -4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,4-bis (4-aminoanilino)- 6-Amino-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-methylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino) Examples thereof include -6-ethylamino-1,3,5-triazine and 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine. Examples of the diamine component that gives the repeating unit of the general formula (I) in which Y ₁ is a divalent group having an aromatic ring containing a fluorine atom include 2,2'-bis (trifluoromethyl) benzidine, 3 , 3'-bis (trifluoromethyl) benzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 '-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane can be mentioned. In addition, preferred diamine compounds include 9,9-bis (4-aminophenyl) fluorene and 4,4'-(((9H-fluorene-9,9-diyl) bis ([1,1'-biphenyl] -5). , 2-diyl)) bis (oxy)) diamine, [1,1': 4', 1 "-terphenyl] -4,4" -diamine, 4,4'-([1,1'-binaphthalene] -2,2'-Diylbis (oxy) diamine can be mentioned. The diamine component may be used alone or in combination of two or more.

When "other Y ₁ " is a divalent group having an alicyclic structure, a divalent group having an alicyclic structure having 4 to 40 carbon atoms is preferable, and at least one aliphatic 4- to 12-membered ring, It is more preferable to have an aliphatic 6-membered ring.

Examples of the divalent group having an alicyclic structure include the following.

（式中、Ｖ_１、Ｖ_２は、それぞれ独立に直接結合、または、２価の有機基であり、ｎ_２１～ｎ_２６は、それぞれ独立に０～４の整数を表し、Ｒ_８１～Ｒ_８６は、それぞれ独立に炭素数１～６のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基であり、Ｒ_９１、Ｒ_９２、Ｒ_９３は、それぞれ独立に 式：－ＣＨ_２－、－ＣＨ＝ＣＨ－、－ＣＨ_２ＣＨ_２－、－Ｏ－、－Ｓ－で表される基よりなる群から選択される１種である。）

(In the formula, V ₁ and V ₂ are independently directly bonded or divalent organic groups, and n ₂₁ to n ₂₆ each independently represent an integer of 0 to 4, and R ₈₁ to R ₈₆ . Are independently alkyl groups, halogen groups, hydroxyl groups, carboxyl groups, or trifluoromethyl groups having 1 to 6 carbon atoms, and R ₉₁ , R ₉₂ , and R ₉₃ are independently represented by the formulas: -CH _2- , respectively. -CH = CH-, -CH ₂ CH _2- , -O-, -S- is one selected from the group consisting of groups represented by.)

Specific examples of V ₁ and V ₂ include a direct coupling and a divalent group represented by the above formula (5).

As the divalent group having an alicyclic structure, the following ones are particularly preferable because they can achieve both high heat resistance and a low coefficient of linear thermal expansion of the obtained polyimide.

脂環構造を有する２価の基としては、中でも、下記のものが好ましい。

As the divalent group having an alicyclic structure, the following are preferable.

Examples of the diamine component that gives the repeating unit of the general formula (I) in which Y ₁ is a divalent group having an alicyclic structure include 1,4-diaminocyclohexane and 1,4-diamino-2-methylcyclohexane. , 1,4-Diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1, , 4-Diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diamino Cyclobutane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethyloxybicycloheptane, isophoronediamine, diaminotricyclo Decane, diaminomethyltricyclodecane, bis (aminocyclohexyl) methane, bis (aminocyclohexyl) isopropanol, 6,6'-bis (3-aminophenoxy) -3,3,3', 3'-tetramethyl -1,1'-spirobiindan, 6,6'-bis (4-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindan can be mentioned. The diamine component may be used alone or in combination of two or more.

As the tetracarboxylic acid component and the diamine component that give the repeating unit represented by the general formula (I), any of aliphatic tetracarboxylic acids (particularly dianhydride) and / or aliphatic diamines other than the alicyclic type are used. However, the content thereof is preferably less than 30 mol%, more preferably less than 20 mol%, still more preferably less than 10 mol% with respect to 100 mol% of the total of the tetracarboxylic acid component and the diamine component ( (Including 0%) is preferable.

As "other Y ₁ ", the structure represented by the formula (4), specific compounds include p-phenylenediamine, 3,3'-bis (trifluoromethyl) benzidine, m-trizine, 4,4'. -By containing a diamine compound such as bis (4-aminophenoxy) biphenyl, the transparency of the obtained polyimide film may be improved. Further, as "other Y ₁ ", the structure represented by the formula (3B), and as a specific compound, a diamine compound such as 9,9-bis (4-aminophenyl) fluorene is contained to obtain Tg. It may be possible to improve or reduce the retardation in the film thickness direction.

The polyimide precursor can be produced from the above-mentioned tetracarboxylic acid component and diamine component. The polyimide precursor used in the present invention (a polyimide precursor containing at least one of the repeating units represented by the above formula (I)) has a chemical structure taken by _R1 and _R2 .
1) Polyamic acid (R ₁ and R ₂ are hydrogen),
2) Polyamic acid ester (at least a part of R ₁ and R ₂ is an alkyl group),
3) 4) Polyamic acid silyl ester (at least a part of R ₁ and R ₂ is an alkyl silyl group),
Can be classified into. The polyimide precursor can be easily produced by the following production methods for each of these categories. However, the method for producing the polyimide precursor used in the present invention is not limited to the following production method.

1) In the polyamic acid polyimide precursor, the tetracarboxylic acid dianhydride as the tetracarboxylic acid component and the diamine component are substantially equimolar, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [molar of the diamine component]. Number / number of moles of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, and suppresses imidization at a relatively low temperature of, for example, 120 ° C. or lower. By reacting while reacting, it can be suitably obtained as a polyimide precursor solution.

More specifically, but not limited to, the diamine is dissolved in an organic solvent or water, and the tetracarboxylic dianhydride is gradually added while stirring to this solution, and the temperature is 0 to 120 ° C., preferably 5. A polyimide precursor can be obtained by stirring in the range of about 80 ° C. for 1 to 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so that the polyimide precursor may not be stably produced. The order of adding diamine and tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor tends to increase. It is also possible to reverse the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method, which is preferable because the precipitates are reduced. When water is used as the solvent, imidazoles such as 1,2-dimethylimidazole or a base such as triethylamine is preferably 0.8 times equivalent to the carboxyl group of the polyamic acid (polyimide precursor) to be produced. It is preferable to add in the above amount.

2) Polyamic acid ester Tetracarboxylic acid dianhydride is reacted with an arbitrary alcohol to obtain a diester dicarboxylic acid, which is then reacted with a chlorination reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. A polyimide precursor can be obtained by stirring the diester dicarboxylic acid chloride and diamine at −20 to 120 ° C., preferably −5 to 80 ° C. for 1 to 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so that the polyimide precursor may not be stably produced. Further, a polyimide precursor can be easily obtained by dehydrating and condensing a diesterdicarboxylic acid and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.

Since the polyimide precursor obtained by this method is stable, purification such as reprecipitation can be performed by adding a solvent such as water or alcohol.

3) Polyamic acid silyl ester (indirect method)
A diamine is reacted with a silylating agent in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and the tetracarboxylic dianhydride is gradually added while stirring, and the temperature is 0 to 120 ° C, preferably 5 to 80 ° C. A polyimide precursor can be obtained by stirring for about 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so that the polyimide precursor may not be stably produced.

4) Polyamic acid silyl ester (direct method)
A polyimide precursor is obtained by mixing the polyamic acid solution obtained by the method 1) with a silylating agent and stirring at 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so that the polyimide precursor may not be stably produced.

When a chlorine-free silylating agent is used as the silylating agent used in the method 3) and the method 4), it is not necessary to purify the silylated polyamic acid or the obtained polyimide. Suitable. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they do not contain a fluorine atom and are low in cost.

Further, in the diamine silylation reaction of the method 3), an amine-based catalyst such as pyridine, piperidine, or triethylamine can be used to promote the reaction. This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.

The solvent used in preparing the polyimide precursor is water or, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3. -Dimethyl-2-imidazolidinone, dimethyl sulfoxide and other aprotic solvents are preferable, and any kind of solvent can be used without any problem as long as the raw material monomer component and the resulting polyimide precursor are dissolved. It is not limited to its structure. As the solvent, water, an amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone , Γ-Caprolactone, ε-caprolactone, cyclic ester solvent such as α-methyl-γ-butyrolactone, carbonate solvent such as ethylene carbonate and propylene carbonate, glycol solvent such as triethylene glycol, m-cresol, p-cresol, 3 -Pharmonic solvents such as chlorophenol and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably adopted. In addition, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran. , Dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorbenzene, turpen, mineral spirit, petroleum Nafsa-based solvents and the like can also be used. The solvent may be used in combination of a plurality of types.

The production of the polyimide precursor is not particularly limited, but the reaction is carried out by charging a monomer and a solvent at a concentration such that the solid content concentration (polyimide-equivalent mass concentration) of the polyimide precursor is, for example, 5 to 45% by mass.

The logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in the N-methyl-2-pyrrolidone solution at a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more, more preferably 0.3 dL /. It is preferably g or more, particularly preferably 0.4 dL / g or more. When the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the mechanical strength and heat resistance of the obtained polyimide are excellent.

<Imidazole compound>
The polyimide precursor composition contains at least one imidazole compound selected from 2-phenylimidazole and benzimidazole.

The content of the imidazole compound in the polyimide precursor composition can be appropriately selected in consideration of the balance between the addition effect and the stability of the polyimide precursor composition. The amount of the imidazole compound is preferably more than 0.01 mol and less than 1 mol per 1 mol of repeating unit of the polyimide precursor. If the content of the imidazole compound is too low, mechanical properties such as elongation at break may be reduced, while if the content of the imidazole compound is too high, the storage stability of the polyimide precursor composition deteriorates. In some cases.

The content of the imidazole compound is more preferably 0.02 mol or more, still more preferably 0.025 mol or more, still more preferably 0.05 mol or more, and more preferably 0.02 mol or more, based on 1 mol of the repeating unit. It is preferably 0.8 mol or less, even more preferably 0.6 mol or less, and even more preferably 0.4 mol or less.

Although Patent Document 6 (International Publication No. 2015/08158) describes a polyimide precursor composition containing an imidazole compound, a polyimide precursor containing 2-phenylimidazole and / or benzimidazole is described. There is no disclosure about the excellent storage stability of the composition. Further, in the examples of the same document, 400 nm light of a polyimide film produced from a composition containing 2-phenylimidazole or benzimidazole as compared with 1,2-dimethylimidazole, 1-methylimidazole and 2-methylimidazole. It has been shown that the permeability is reduced. On the other hand, it is produced from a composition in which 2-phenylimidazole and / or benzimidazole is combined with a preferable polyimide precursor of the present invention (70 mol% or more of X ₁ is derived from CpODA and 70 mol% or more of Y ₁ is derived from DABAN). The polyimide film had improved transparency, and contrary to the disclosure of Patent Document 6, a light transmittance of 400 nm equal to or higher than that of 2-methylimidazole was obtained. It was also confirmed that 2-phenylimidazole and benzimidazole are more effective in lowering the linear expansion coefficient than other imidazoles.

<Formulation of polyimide precursor composition>
The polyimide precursor composition used in the present invention contains at least one polyimide precursor, at least one imidazole compound described above, and a solvent.

As the solvent, the above-mentioned solvent described as the solvent used when preparing the polyimide precursor can be used. Usually, the solvent used in preparing the polyimide precursor can be used as it is, that is, as the polyimide precursor solution, but it may be diluted or concentrated as necessary. The imidazole compound is dissolved and present in the polyimide precursor composition. The concentration of the polyimide precursor is not particularly limited, but is usually 5 to 45% by mass in terms of polyimide-equivalent mass concentration (solid content concentration). Here, the polyimide reduced mass is the mass when all of the repeating units are completely imidized.

The viscosity (rotational viscosity) of the polyimide precursor of the present invention is not particularly limited, but the rotational viscosity measured at a temperature of 25 ° C. and a shear rate of 20 sec ^-1 using an E-type rotational viscometer is 0.01 to 1000 Pa · sec. Is preferable, and 0.1 to 100 Pa · sec is more preferable. In addition, thixotropic properties can be imparted as needed. When the viscosity is in the above range, it is easy to handle when coating or forming a film, repelling is suppressed, and the leveling property is excellent, so that a good film can be obtained.

The polyimide precursor composition of the present invention can be used as a chemical imidizing agent (acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinolin), an antioxidant, an ultraviolet absorber, a filler (silica, etc.), if necessary. (Inorganic particles, etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame-retardant materials, defoaming agents, leveling agents, polyimide control agents (fluid aids), and the like.

The polyimide precursor composition can be prepared by adding a solution of an imidazole compound or a solution of an imidazole compound to the polyimide precursor solution obtained by the method as described above and mixing them. The tetracarboxylic acid component and the diamine component may be reacted in the presence of the imidazole compound.

<< Manufacture of polyimide film / base material laminate and flexible electronic device >>
In the polyimide film / base material laminate of the present invention, (a) a step of applying a polyimide precursor composition onto a base material, (b) the polyimide precursor is heat-treated on the base material, and the base material is used. It can be manufactured by a step of manufacturing a laminate (polyimide film / base material laminate) in which a polyimide film is laminated on top. The method for manufacturing a flexible electronic device of the present invention uses the polyimide film / base material laminate produced in the steps (a) and (b), and further steps, that is, (c) on the polyimide film of the laminate. It also has a step of forming at least one layer selected from a conductor layer and a semiconductor layer, and (d) a step of peeling the base material and the polyimide film.

The polyimide precursor composition that can be used in the method of the present invention contains a polyimide precursor, an imidazole compound and a solvent. As the imidazole compound, those described in the above-mentioned imidazole compound section can be used. As the polyimide precursor, those described in the section of the polyimide precursor composition can be used. The polyimide precursor described as preferable in the section of the polyimide precursor composition is also preferable in the method of the present invention, but is not particularly limited.

First, in the step (a), a polyimide film is formed by casting a polyimide precursor composition on a substrate, imidizing and dessolving it by heat treatment, and a laminate (polyimide) of the substrate and the polyimide film. Film / substrate laminate) is obtained.

As the base material, a heat-resistant material is used, for example, a plate-like material such as a ceramic material (glass, alumina, etc.), a metal material (iron, stainless steel, copper, aluminum, etc.), a semiconductor material (silicon, compound semiconductor, etc.) or the like. A sheet-like substrate, or a film such as a heat-resistant plastic material (polyimide, etc.) or a sheet-like substrate is used. Generally, a flat and smooth plate shape is preferable, and generally, a glass substrate such as soda lime glass, borosilicate glass, non-alkali glass, and sapphire glass; a semiconductor (including compound semiconductor) substrate such as silicon, GaAs, InP, and GaN; Metallic substrates such as iron, stainless steel, copper and aluminum are used.

A glass substrate is particularly preferable in the present invention. Glass substrates that are flat, smooth, and have a large area have been developed and are easily available. The problem of warpage becomes apparent especially as the area of the substrate becomes larger, and the glass substrate is relatively prone to warp in terms of rigidity. Therefore, by applying the present invention, it is possible to solve the problem when the glass substrate is used. The thickness of the plate-shaped base material such as a glass substrate is not limited, but is, for example, 20 μm to 4 mm, preferably 100 μm to 2 mm from the viewpoint of ease of handling. The size of the plate-shaped base material is not particularly limited, but one side (long side in the case of a rectangle) is, for example, about 100 mm to 4000 mm, preferably about 200 mm to 3000 mm, and more preferably about 300 mm to 2500 mm. Is.

The base material such as these glass substrates may have an inorganic thin film (for example, a silicon oxide film) or a resin thin film formed on the surface thereof.

The method of casting the polyimide precursor composition onto the substrate is not particularly limited, but for example, a slit coating method, a die coating method, a blade coating method, a spray coating method, an inkjet coating method, a nozzle coating method, a spin coating method, and screen printing. Examples thereof include conventionally known methods such as a method, a bar coater method, and an electrodeposition method.

In the step (b), the polyimide precursor composition is heat-treated on the substrate and converted into a polyimide film to obtain a polyimide film / substrate laminate. The heat treatment conditions are not particularly limited, but are, for example, after drying in a temperature range of 50 ° C. to 150 ° C., the maximum heating temperature is, for example, 150 ° C. to 600 ° C., preferably 200 ° C. to 550 ° C., and more preferably 250 ° C. It is preferable to treat at ~ 500 ° C. The heat treatment conditions when the polyimide solution is used are not particularly limited, but the maximum heating temperature is, for example, 100 ° C to 600 ° C, preferably 150 ° C or higher, more preferably 200 ° C or higher, and preferably 500 ° C. Below, it is more preferably 450 ° C. or lower.

The thickness of the polyimide film is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 5 μm or more. If the thickness is less than 1 μm, the polyimide film cannot maintain sufficient mechanical strength and may not be able to withstand stress and may be broken when used as a flexible electronic device substrate, for example. The thickness of the polyimide film is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 20 μm or less. If the thickness of the polyimide film is increased, it may be difficult to reduce the thickness of the flexible device. The thickness of the polyimide film is preferably 2 to 50 μm in order to make the film thinner while maintaining sufficient resistance as a flexible device.

In one embodiment, the polyimide film has a 400 nm light transmittance of preferably 50% or more, more preferably 70% or more, still more preferably 75% or more, and most preferably 80% or more when measured with a film having a thickness of 10 μm. be.

In the present invention, the polyimide film / base material laminate is characterized by having a small warp. The details of the measurement will be described later in the section << Evaluation of warpage, measurement of residual stress >>, but in one embodiment, the characteristics of the polyimide film are the same as that of the polyimide film in the polyimide film / silicon substrate (wafer) laminate. When evaluated by the residual stress between the silicon substrates, the residual stress is preferably less than 27 MPa, more preferably less than 25 MPa. However, it is assumed that the polyimide film is left at 23 ° C. in a dry state.

Using this as a base material, 6th generation Corning's Eagle-XG (registered trademark) (glass substrate, vertical size: 1500 mm, horizontal size: 1850 mm, diagonal size: 2382 mm, thickness: 0.5 mm, elastic modulus: In terms of 73.6 GPa), the size of the warp of the 10 μm-thick polyimide film / glass substrate laminate is preferably less than 64 mm, more preferably less than 58 mm in diagonal size. Here, the magnitude of the warp is the distance from the plane to the peripheral portion when the laminated body is placed on the plane as shown in FIG.

Further, in one embodiment of the present invention, the polyimide film has a breaking elongation of a film having a thickness of 10 μm, preferably 10% or more.

Further, in a different preferred embodiment of the present invention, the breaking strength of the polyimide film is preferably 150 MPa or more, more preferably 170 MPa or more, still more preferably 180 MPa or more, still more preferably 200 MPa or more, still more preferably 210 MPa or more. Is. As the breaking strength, a value obtained from a film having a film thickness of, for example, about 5 to 100 μm can be used.

It is particularly preferable that the above preferable properties for the polyimide film and the laminate are satisfied at the same time.

The polyimide film in the polyimide film / base material laminate may have a second layer such as a resin film or an inorganic film on the surface. That is, after forming a polyimide film on a substrate, a second layer may be laminated to form a flexible electronic device substrate. It is preferable to have at least an inorganic film, and particularly preferably one that functions as a barrier layer for water vapor, oxygen (air), or the like. Examples of the water vapor barrier layer include silicon nitride (SiN _x ), silicon oxide (SiO _x ), silicon nitride (SiO _{x Ny} ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TIO ₂ ), and zirconium oxide. Examples thereof include an inorganic film containing an inorganic substance selected from the group consisting of metal oxides such as (ZrO ₂ ), metal nitrides and metal oxynitrides. Generally, as the film forming method of these thin films, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method and an ion plating method, and a chemical vapor deposition method such as a plasma CVD method and a catalytic chemical vapor deposition method (Cat-CVD method) are used. The method (chemical vapor deposition method) is known. The second layer may be a plurality of layers.

When the second layer is a plurality of layers, it is also possible to combine the resin film and the inorganic film. For example, the barrier layer / polyimide layer / barrier layer is formed on the polyimide film in the polyimide film / base material laminate. Examples include forming a three-layer structure.

In the step (c), the polyimide / base material laminate obtained in the step (b) is used on a polyimide film (including a polyimide film on which a second layer such as an inorganic film is laminated on the surface). It forms at least one layer selected from the conductor layer and the semiconductor layer. These layers may be formed directly on a polyimide film (including a laminate of a second layer) or on a laminate of other layers required for the device, i.e. indirectly. good.

As the conductor layer and / or the semiconductor layer, an appropriate conductor layer and (inorganic, organic) semiconductor layer are selected according to the elements and circuits required by the target electronic device. When forming at least one of the conductor layer and the semiconductor layer in the step (c) of the present invention, it is also preferable to form at least one of the conductor layer and the semiconductor layer on the polyimide film on which the inorganic film is formed.

The conductor layer and the semiconductor layer include both those formed on the entire surface of the polyimide film and those formed on a part of the polyimide film. The present invention may immediately shift to the step (d) after the step (c), or after forming at least one layer selected from the conductor layer and the semiconductor layer in the step (c), further device structure is formed. After forming, the process may proceed to step (d).

When manufacturing a TFT liquid crystal display device as a flexible device, for example, a metal wiring, a TFT made of amorphous silicon or polysilicon, and a transparent pixel electrode are formed on a polyimide film having an inorganic film formed on the entire surface, if necessary. The TFT includes, for example, a gate metal layer, a semiconductor layer such as an amorphous silicon film, a gate insulating layer, wiring connected to a pixel electrode, and the like. On top of this, a structure required for a liquid crystal display can also be formed by a known method. Further, a transparent electrode and a color filter may be formed on the polyimide film.

In the case of manufacturing an organic EL display, for example, a TFT is formed on a polyimide film having an inorganic film formed on the entire surface, for example, in addition to a transparent electrode, a light emitting layer, a hole transport layer, an electron transport layer, etc. can do.

Since the polyimide film preferable in the present invention is excellent in various properties such as heat resistance and toughness, the method for forming the circuit, element, and other structures required for the device is not particularly limited.

Next, in step (d), the base material and the polyimide film are peeled off. The peeling method may be a mechanical peeling method in which physical peeling is performed by applying an external force, or a so-called laser peeling method in which laser light is irradiated from the substrate surface to peel.

The device is completed by further forming or incorporating the structure or component required for the device into the (semi) product using the polyimide film after peeling the base material as the substrate.

<< Evaluation of warpage, measurement of residual stress >>
FIG. 1 schematically shows the warp of the polyimide film / base material laminate in which the polyimide film 1 is formed on the base material 2. The warp of the polyimide film / base material laminate depends on the elastic modulus of the base material. Even with the same type of substrate, the "warp value" differs depending on the thickness and size.

Further, according to the study of the present inventor, since the polyimide is stretched by absorbing moisture, the degree of warpage of the polyimide film / base material laminate differs depending on the dry state of the polyimide film. In particular, when the evaluation is performed in the environmental atmosphere and the environmental temperature, the polyimide film tends to absorb moisture and the warp of the laminate tends to be small, whereas in the production of flexible electronic devices, it is under vacuum or reduced pressure or is inert. Since the film formation is carried out in an atmosphere and the transportation and storage are also carried out in a dry atmosphere, the warp of the laminated body becomes large. In other words, it is not possible to accurately evaluate the warp that is a problem in the manufacture of electronic devices by measuring in the environmental atmosphere and environmental temperature. Therefore, it is preferable to measure the warp (or residual stress) in a dry state of the polyimide film. Therefore, it is conceivable to place the entire measuring device in a dry atmosphere, but this is not practical because the device becomes large and it takes time for the polyimide film to reach an equilibrium state.

One aspect of the present invention made to solve such a problem is.
(1) A step of preparing a polyimide film / reference base material laminate in which a polyimide film is formed on a reference base material.
(2) A step of measuring the radius of curvature (warp) of the polyimide film / reference base material laminate at a plurality of measurement temperatures of 80 ° C. or higher.
(3) A step of calculating the residual stress at the measured temperature between the polyimide film in the polyimide film / reference base material laminate and the reference base material based on the measured radius of curvature (warp), and (4) a plurality. The present invention relates to a method for evaluating the residual stress of a polyimide film / base material laminate, which comprises a step of obtaining a residual stress at a predetermined temperature based on the residual stress at the measured temperature.

The reason for using the "reference base material" in the step (1) is that the warp of the polyimide film / base material laminate differs depending on the base material as described above. This is because it is preferable to use a reference base material (hereinafter referred to as a reference base material) suitable for the above. Since the main object of the present invention is to evaluate the warp of the polyimide film / glass substrate laminate, the following measurements and evaluations can be performed using the glass substrate. In, a silicon substrate (wafer) having a predetermined thickness was used as a reference base material. This is because the reflectance of the surface of the silicon substrate is high, and the warp can be easily measured by an optical method. In particular, the selection is not limited to the silicon substrate, and can be selected in consideration of the measuring device and method.

The polyimide film / reference base material laminate is coated on the reference base material with (a) the polyimide precursor composition according to the above-mentioned method for producing the polyimide film / base material laminate, and (b) on the reference base material. The polyimide precursor can be heat-treated to be produced by laminating a polyimide film on a reference base material, and this can be used as a measurement sample.

Next, in the step (2), the warp is measured at a relatively high temperature in which the polyimide film is in a dry state. The "relatively high temperature in a dry state" is, for example, 80 ° C. or higher, and 100 ° C. or higher is particularly preferable. The upper limit of the temperature is Tg of polyimide, and when Tg is not observed, the decomposition temperature is the upper limit. This is because the change in elastic modulus is small up to Tg, but the elastic modulus changes greatly when it exceeds Tg, so that it is not suitable as a measurement point to be extrapolated to, for example, room temperature in the next step (4). Usually, it is 250 ° C. or lower, preferably 200 ° C. or lower. Generally, the range of 100 ° C. to 200 ° C., for example, 100 ° C. to 150 ° C. is preferable.

Therefore, in the method of this embodiment, the warp may be measured at a plurality of different temperatures in such a temperature range, preferably at three or more different temperatures, and more preferably at four or more different temperatures. Further, although it depends on the measuring method and the measuring device, in order to improve the measurement accuracy, it is preferable to measure a plurality of times, for example, 3 times or more, for example, about 10 times or more at the same temperature to obtain an average value.

As the environment of the measuring method, the measuring device may be measured in a dry environment such as in dry air and an inert gas, but the environment in which the measuring device is placed is, for example, a normal environmental atmosphere and an environmental temperature (for example,). Even at 15 ° C to 30 ° C and relative humidity of 30 to 60%), the measurement sample and its surroundings become hot as described above, so that the measurement sample is placed in an extremely low humidity environment.

"Warp" can be measured by various methods and can be expressed by various indexes. A method of optically obtaining the light (for example, laser light) from the reflection angle or the like is convenient and preferable. "Warp" can be expressed by the radius of curvature as an example.

Next, in the step (3), the residual stress S is calculated according to the mathematical formula 1 based on the measured value of the warp obtained in the step (2).

here,
E / (1-ν): Biaxial elastic modulus (Pa) of the substrate (reference substrate: silicon wafer),
(100) For silicon, 1.805E11Pa,
h: Substrate thickness (m)
t: Polyimide film thickness (m)
R: Radius of curvature (m) of the measurement sample
1 / R = 1 / R _2-1 / R ₁
R ₁ : Radius of curvature of the substrate (silicon wafer) before film formation R ₂ : Radius of curvature after film formation S: Mean value of residual stress (Pa)

Next, in the step (4), the residual stress at a predetermined temperature is obtained based on the residual stress at a plurality of measured temperatures calculated in the step (3). The predetermined temperature is not a particularly fixed temperature, but a target temperature (temperature-of-interest) that can be selected according to the purpose, and may be a temperature at which the laminate is used and warpage is a problem. At room temperature, for example, 23 ° C. may be adopted.

In the example of FIG. 2, the residual stress obtained from five different measurement temperatures of 100 ° C. or higher is plotted on a graph with the temperature on the horizontal axis and the residual stress on the vertical axis. The predetermined temperature is 23 ° C. in this example. The method for obtaining the residual stress at a predetermined temperature from the measurement point is not particularly limited, but usually, as shown in FIG. 2, a linear approximation (by the least squares method) is performed, and the residual stress at 23 ° C is obtained by extrapolating to 23 ° C. be able to.

As described above, the characteristics of the polyimide film can be evaluated by the residual stress at 23 ° C. between the polyimide film and the silicon substrate (as a reference base material).

Further, in order to estimate the warp of the polyimide film / target base material laminate using the target base material (for example, glass substrate) actually used for device manufacturing, the following is performed. First, the radius of curvature R of the warp generated in the polyimide film / target base material laminate is obtained by using the following mathematical formula 2.

here,
E: Tension elastic modulus (Pa) of the target substrate
h: Thickness of target substrate (m)
t: Polyimide film thickness (m)
S: Residual stress (Pa) at 23 ° C (predetermined temperature) obtained for the reference substrate
R: Radius of curvature (m)

By substituting the radius of curvature calculated from Equation 2 into Equation 3, the magnitude of the warp (W) shown in FIG. 1 can be calculated and estimated.

here,
L: Length (m) of the target base material, for example, diagonal distance, etc.
W: The size of the warp

According to the method for evaluating the residual stress of the polyimide film / base material laminate of the present embodiment as described above, the influence of moisture absorption of the polyimide film can be eliminated, and the following advantageous effects can be obtained. First, when the polyimide film in the laminated body is in a hygroscopic state, the warp is relatively small, which is often different from the warp generated in the actual process, but this embodiment enables appropriate evaluation. In addition, stable evaluation has become possible without being affected by the measurement environment. Further, since the difference in warpage between the hygroscopic state and the dry state differs depending on the composition of the polyimide (because the hygroscopicity differs depending on the composition), the relative evaluation was meaningless in the hygroscopic state. You can now make accurate comparisons.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

In each of the following examples, the evaluation was performed by the following method.

<Evaluation of polyimide precursor solution (varnish)>
[Storage stability]
If the varnish is stored at 23 ° C and is in a fluid and uniform state after 30 days, ○,
If it becomes cloudy or gelled after 30 days, it is marked as x.

<Evaluation of polyimide film>
[400 nm light transmittance]
Using an ultraviolet-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation), the light transmittance of a polyimide film having a film thickness of about 10 μm at 400 nm was measured.

[Elastic modulus, breaking elongation, breaking strength]
A polyimide film with a thickness of about 10 μm was punched into a dumbbell shape of IEC450 standard to make a test piece, and using TENSILON manufactured by ORIENTEC, the initial elastic modulus, breaking elongation, and breaking were achieved with a chuck spacing of 30 mm and a tensile speed of 2 mm / min. The intensity was measured.

[Coefficient of linear thermal expansion (CTE)]
A polyimide film with a thickness of about 10 μm is cut into strips with a width of 4 mm to make test pieces, and TMA / SS6100 (manufactured by SII Nanotechnology Co., Ltd.) is used. The temperature was raised to 500 ° C. in minutes. From the obtained TMA curve, the coefficient of linear thermal expansion from 150 ° C to 250 ° C was obtained.

[5% weight loss temperature]
Using a polyimide film having a film thickness of about 10 μm as a test piece, the temperature was raised from 25 ° C. to 600 ° C. in a nitrogen stream at a heating rate of 10 ° C./min using a calorimeter measuring device (Q5000IR) manufactured by TA Instruments. From the obtained weight curve, the 5% weight loss temperature was determined.

<Evaluation of polyimide film / substrate laminate>
The warp of the polyimide film / silicon wafer laminate was measured using FLX-2320 manufactured by KLA Tencor. The radius of curvature of a single silicon wafer is measured in advance in an environment of 23 ° C. and 50% RH. Then, a polyimide film is formed on the silicon wafer. The radius of curvature of the laminate was measured and the residual stress was calculated. When the radius of curvature of the polyimide film / reference substrate laminate was measured in a heated state, the radius of curvature of the silicon wafer alone was measured at the same temperature.

<Raw materials>
The abbreviations, purity, etc. of the raw materials used in each of the following examples are as follows.

[Diamine component]
DABAN: 4,4'-diaminobenzanilide PPD: p-phenylenediamine BABP: 4,4'-bis (4-aminophenoxy) biphenyl TPE-Q: 1,4-bis (4-aminophenoxy) benzeneBAFL: 9 , 9-bis (4-aminophenyl) fluorene TFMB: 2,2'-bis (trifluoromethyl) benzidine m-TD: m-tridin

[Tetracarboxylic acid component]
CpODA: Norbornan-2-spiro-α-cyclopentanone-α'-spiro-2 "-norbornan-5,5", 6,6 "-tetracarboxylic acid dianhydride DNDAxx: (4arH, 8acH) -decahydro- 1t, 4t: 5c, 8c-dimethanonaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid dianhydride PMDA-H: cyclohexanetetracarboxylic acid dianhydride CBDA: cyclobutanetetracarboxylic acid dianhydride

[Imidazole compound]
2-Pz: 2-Phenylimidazole Bz: Benzimidazole 2-Mz: 2-Methylimidazole

[solvent]
NMP: N-methyl-2-pyrrolidone

Table 1-1 shows the tetracarboxylic acid component and the diamine component used in Examples and Comparative Examples, and Table 1-2 shows the structural formulas of the imidazole compounds used in Examples and Comparative Examples.

<Example 1>
[Preparation of polyimide precursor composition]
2.27 g (0.010 mol) of DABAN was placed in a reaction vessel substituted with nitrogen gas, and N-methyl-2-pyrrolidone was added, and the total mass of the charged monomers (total of diamine component and carboxylic acid component) was 16% by mass. A certain amount of 32.11 g was added, and the mixture was stirred at 50 ° C. for 1 hour. 3.84 g (0.010 mol) of CpODA was gradually added to this solution. The mixture was stirred at 70 ° C. for 4 hours to obtain a uniform and viscous polyimide precursor solution.

2-Phenylimidazole as an imidazole compound was dissolved in 4-fold mass of N-methyl-2-pyrrolidone to obtain a uniform solution having a solid content concentration of 2-phenylimidazole of 20% by mass. The solution of the imidazole compound and the polyimide precursor solution synthesized above were mixed so that the amount of the imidazole compound was 0.025 mol per 1 mol of the repeating unit of the polyimide precursor, and the mixture was stirred at room temperature for 3 hours. A uniform and viscous polyimide precursor composition was obtained.

[Manufacturing of polyimide film / base material laminate]
In order to produce a polyimide film / base material laminate for evaluation of a polyimide film, a 6-inch Eagle-XG® (registered trademark) (500 μm thickness) manufactured by Corning Inc. was used as a glass substrate. The polyimide precursor composition is applied onto a glass substrate with a spin coater, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), the polyimide film is thermally imidized by heating it from room temperature to 415 ° C. on the glass substrate as it is. / A substrate laminate was obtained. The polyimide film was peeled off from the glass substrate by immersing the laminate in hot water, and after drying, the characteristics of the polyimide film were evaluated. The film thickness of the polyimide film is about 10 μm.

[Manufacturing of polyimide film / reference base material laminate]
A 6-inch silicon wafer (625 μm thick, (100) substrate) was used as a reference base material for evaluating the polyimide film. The polyimide precursor composition is applied onto a silicon wafer with a spin coater, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), the polyimide film is thermally imidized by heating from room temperature to 415 ° C. on the silicon wafer as it is. / A reference substrate laminate was obtained. The film thickness of the polyimide film in the laminate is about 10 μm.

The radius of curvature of the obtained polyimide film / reference substrate laminate was measured at temperatures of 150 ° C., 140 ° C., 130 ° C., 120 ° C. and 110 ° C. It was measured 20 times at each temperature and the average value was calculated. The residual stress at each temperature was calculated from the obtained radius of curvature, and the residual stress at 23 ° C. was obtained from the linear approximation by the least squares method. Further, the residual stress was obtained from the radius of curvature of the warp measured in an environment of 23 ° C. and 50% RH without heating. The results are shown in Tables 2 to 4. 6th generation glass substrate (target base material) (Eagle-XG (registered trademark), vertical size: 1500 mm, horizontal size: 1850 mm, diagonal size: 2382 mm, thickness: 0.5 mm, elastic modulus: 73.6 GPa ) Is used to calculate the value of warpage that occurs when a polyimide film / base material laminate is manufactured, and the values are shown in Tables 2 to 4.

<Examples 2 to 15, Comparative Examples 1 to 14>
In Example 1, the polyimide film / reference was the same as in Example 1 except that the tetracarboxylic acid component, the diamine component, the imidazole compound, and the maximum temperature at the time of film formation were changed to the compounds shown in Tables 2 to 5. A substrate laminate was produced, the warp of the laminate was measured in the same manner as in Example 1, and the residual stress at 23 ° C. was determined. The results are shown in Tables 2 to 5. Further, in Tables 2 to 4, the warp estimated for the polyimide film / substrate laminate using the 6th generation glass substrate (Eagle-XG (registered trademark) 500 μm thickness, elastic modulus: 73.6 GPa) is also used. The values of are also shown.

<Reference Examples 1 to 3>
Table 4 shows the results of evaluating the characteristics of the polyimide film produced on a silicon wafer, not on a glass substrate.

<Examples 16 to 22>
In Example 1, a glass substrate was used in the same manner as in Example 1 except that the tetracarboxylic dian component, the diamine component, and the imidazole compound, and the maximum temperature at the time of film formation were changed to the compounds and conditions shown in Table 6. Manufactured a polyimide film / base material laminate. The polyimide film was peeled from the glass substrate in the same manner as in Example 1, dried, and then the characteristics of the polyimide film were evaluated. The results are shown in Table 6. In the qualitative observation of the polyimide film / substrate laminate, the size of the warp was equivalent to that of Examples 2 and 3. Table 6 shows the residual stress and warpage values measured in the same manner as in Example 1.

The present invention can be suitably applied to the manufacture of flexible electronic devices such as liquid crystal displays, organic EL displays, display devices such as electronic paper, solar cells and light receiving devices such as CMOS.

Claims (14)

A polyimide precursor represented by the following general formula (I),
At least one imidazole compound and a solvent contained in an amount in the range of more than 0.01 mol to less than 1 mol and selected from 2-phenylimidazole and benzimidazole with respect to 1 mol of the repeating unit of the polyimide precursor. A polyimide precursor composition comprising.

(In the general formula I, X ₁ is a tetravalent aliphatic group or an aromatic group, Y ₁ is a divalent aliphatic group or an aromatic group, and R ₁ and R ₂ are independent of each other and hydrogen. An atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, wherein 70 mol% or more of X ₁ is the formula (1-1) :.

In the structure represented by, 60 mol% or more and less than 100 mol% of Y ₁ is the formula (D-1) and / or (D-2) :.

It is a structure represented by. ) The formula (G- ₁ )::

(In the formula, m represents 0 to 3, n1 and n2 each independently represent an integer of 0 to 4, and B ₁ and B ₂ independently represent an alkyl group, a halogen group or a carbon having 1 to 6 carbon atoms. Represents one selected from the group consisting of fluoroalkyl groups of numbers 1-6, where X is independently, directly bonded, or represented by the formulas: -NHCO-, -CONH-, -COO-, -OCO-. Represents one selected from the group consisting of groups, except for the formulas (D-1) and (D-2).
The polyimide precursor composition according to claim 1, which has a structure represented by. More than ₀ mol% and 40 mol% or less of Y1 in the formula (I) are the formulas (B-1) and / or (B-2):

The polyimide precursor composition according to claim 2, which has a structure represented by. The one according to any one of claims 1 to 3, wherein the polyimide film obtained from this polyimide precursor composition has a light transmittance of 75% or more at a wavelength of 400 nm in a film having a thickness of 10 μm. Polyimide precursor composition. The polyimide precursor composition according to any one of claims 1 to 3, wherein the polyimide film obtained from this polyimide precursor composition has a breaking elongation of a film having a thickness of 10 μm of 10% or more. thing. The polyimide precursor composition according to any one of claims 1 to 5, wherein 90 mol% or more of X ₁ has a structure represented by the above formula (1-1). The polyimide precursor composition is applied onto a silicon wafer to imidize it to produce a polyimide film / silicon wafer laminate having a thickness of 10 μm, and the polyimide film / silicon wafer laminate is used at 80 ° C. or higher, a glass transition temperature, and a glass transition temperature. Claims 1 to give a polyimide film in which the residual stress at 23 ° C. is less than 27 MPa when the residual stress between the polyimide film and the silicon wafer obtained at a plurality of temperatures in the range of less than the lower decomposition temperature is linearly approximated. Item 6. The polyimide precursor composition according to any one of 6. A polyimide film obtained from the polyimide precursor composition according to any one of claims 1 to 7. A polyimide film obtained from the polyimide precursor composition according to any one of claims 1 to 7.
A polyimide film / base material laminate characterized by having a base material. The laminate according to claim 9, wherein the base material is a glass substrate. (A) A step of applying the polyimide precursor composition according to any one of claims 1 to 7 onto a substrate, and (b) heat-treating the polyimide precursor on the substrate to obtain the above-mentioned A method for producing a polyimide film / substrate laminate, which comprises a step of laminating a polyimide film on a substrate. The manufacturing method according to claim 11, wherein the base material is a glass substrate. (A) A step of applying the polyimide precursor composition according to any one of claims 1 to 7 onto a substrate.
(B) A step of heat-treating the polyimide precursor on the base material to produce a polyimide film / base material laminate in which the polyimide film is laminated on the base material.
(C) Flexible electrons having a step of forming at least one layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminated body, and (d) a step of peeling the base material and the polyimide film. How to make the device. The manufacturing method according to claim 13, wherein the base material is a glass substrate.

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