TW202118813A - Polyimide precursor composition and method for producing flexible electronic device - Google Patents

Abstract

Disclosed is a polyimide precursor composition comprising a polyimide precursor, a phosphorus compound having a P(=O)OH structure or a P(=O)OR (wherein R is an alkyl group having 4 or more carbon atoms) structure, and a solvent. With this composition, it is possible to industrially produce a flexible electronic device using a simple apparatus.

Description

Polyimide precursor composition and manufacturing method of flexible electronic device

The present invention relates to a polyimide precursor composition suitable for use in electronic devices such as substrates of flexible devices, and a method for manufacturing flexible electronic devices.

Polyimide film has been widely used in electrical, electronic device, semiconductor and other fields because of its excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability. On the other hand, in recent years, with the advent of a highly information-oriented society, the development of optical materials such as optical fibers and optical waveguides in the field of optical communications, and optical materials such as liquid crystal alignment films and protective films for color filters in the field of display devices has been continuously promoted. . Especially in the field of display devices, plastic substrates with light weight and excellent flexibility are being actively researched to replace glass substrates, and displays that can be bent or rolled up are being developed.

In displays such as liquid crystal displays and organic EL (Electroluminescence) displays, semiconductor elements such as TFT (Thin Film Transistor) for driving each pixel are formed. Therefore, the substrate is required to have heat resistance and dimensional stability. Polyimide films are expected to be used as substrates for displays due to their excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability.

Polyimide is usually colored yellowish brown, so its use in transmissive devices such as liquid crystal displays with backlights is limited. However, in recent years, a polyimide film with excellent mechanical and thermal properties and excellent transparency has been developed. , And more promising as a substrate for displays (refer to Patent Documents 1 to 3).

Generally, it is difficult for a flexible film to maintain flatness, and therefore it is difficult to uniformly and accurately form semiconductor elements such as TFTs, fine wiring, etc. on the flexible film. For example, Patent Document 4 describes: "A method of manufacturing a flexible device, the flexible device is a display device or a light receiving device, the method of manufacturing the flexible device includes the following steps: combining specific precursor resins A solid polyimide resin film is formed by coating and forming a film on a carrier substrate; forming a circuit on the resin film; and peeling the solid resin film with the circuit formed on the surface from the carrier substrate".

In addition, as a method of manufacturing a flexible device, Patent Document 5 discloses a method including the following steps: forming a polyimide film on a glass substrate to obtain a polyimide film/glass substrate laminate, and After the components and circuits required for the device are formed on the laminate, the laser is irradiated from the glass substrate to peel off the glass substrate. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/011590 [Patent Document 2] International Publication No. 2013/179727 [Patent Document 3] International Publication No. 2014/038715 [Patent Document 4] Japanese Patent Laid-Open No. 2010-202729 [Patent Document 5] International Publication No. 2018/221607 [Patent Document 6] International Publication No. 2012/173204 [Patent Document 7] International Publication No. 2015/080139

[The problem to be solved by the invention]

The advantage of mechanical peeling as described in Patent Document 4 is that it does not require additional equipment and is easy to operate. However, sometimes the peeling strength between the polyimide film and the glass substrate is too high. When the polyimide film is peeled from the glass substrate, it will Cause damage to the components and circuits formed on the polyimide film. On the other hand, the advantage of laser peeling as described in Patent Document 5 is that it can ensure high adhesion between the polyimide film and the glass substrate when forming components and circuits, and reduce the peeling strength during peeling. And the circuit damage is small. However, the above-mentioned laser peeling requires a laser irradiation device or the like, which causes an increase in equipment cost.

However, Patent Document 6 describes the addition of monoethyl phosphate to a polyimide precursor solution obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine. (Example 4), monolauryl phosphate (Example 5), and polyphosphoric acid (Example 6). However, there is no description of the polyphosphate formed on the substrate by adding these phosphorus compounds. The peeling strength of the imide film and the substrate is reduced, and the manufacture of flexible electronic devices.

Furthermore, Patent Document 7 describes an example in which phosphoric acid (Comparative Example 2) and tributyl phosphate (Comparative Example 4) are added to a polyimide precursor solution having specific components as a comparative example, but it is not described at all. By adding the phosphorus compounds, the peeling strength of the polyimide film formed on the substrate and the substrate is reduced.

The present invention was completed in view of the previous problems. The main purpose of the present invention is to provide a polyimide precursor composition and flexible electronics that can be used to manufacture flexible electronic devices by industrially simple devices and steps. The manufacturing method of the device. [Technical means to solve the problem]

The main disclosures of this application are summarized as follows.

1. A polyimide precursor composition, characterized in that it contains: Polyimide precursor; Phosphorus compound, which has a P(=O)OH structure or P(=O)OR (wherein R is an alkyl group with 4 or more carbons) structure, and is relative to the total monomer units of the polyimide precursor , Which is more than 0.001 mol% and less than 5 mol%; and Solvent (However, the following condition (A) is satisfied). (A) The above-mentioned polyimine precursor is not only a polyimine precursor obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine. 2. The composition as described in the above item 1, wherein the content of the phosphorus compound is 0.01 mol% or more relative to the total monomer units of the polyimide precursor. 3. The composition as described in item 1 or 2, wherein the phosphorus compound does not include a compound having an aryl group directly bonded to P. 4. The composition as described in any one of items 1 to 3 above, wherein the molecular weight of the phosphorus compound is less than 400. 5. The composition as described in any one of the above items 1 to 4, characterized in that the polyimide precursor comprises a repeating unit, and the repeating unit is selected from the structure represented by the following general formula (I) , And a structure in which at least one amide structure in the general formula (I) is amide.

(通式(I)中，X₁ 係4價之脂肪族基或芳香族基，Y₁ 係2價之脂肪族基或芳香族基，R₁ 及R₂ 相互獨立地為氫原子、碳數1～6之烷基或碳數3～9之烷基矽烷基) 6.如上述第5項所記載之組合物，其特徵在於：相對於總重複單元，X₁ 係具有脂環結構之4價基且Y₁ 係具有脂環結構之2價基的通式(I)所示之重複單元之含量為50莫耳%以下。 7.如上述第5項所記載之組合物，其特徵在於：通式(I)中之X₁ 係具有芳香族環之4價基，Y₁ 係具有芳香族環之2價基。 8.如上述第5項所記載之組合物，其特徵在於：通式(I)中之X₁ 係具有脂環結構之4價基，Y₁ 係具有芳香族環之2價基。 9.如上述第5項所記載之組合物，其特徵在於：通式(I)中之X₁ 係具有芳香族環之4價基，Y₁ 係具有脂環結構之2價基。 10.如上述第5項所記載之組合物，其特徵在於：以在總重複單元中超過60%之比率含有通式(I)之X₁ 係具有脂環結構之4價基的重複單元(但，相對於總重複單元，X₁ 係具有脂環結構之4價基且Y₁ 係具有脂環結構之2價基的通式(I)所示之重複單元之含量為50莫耳%以下)。 11.一種可撓性電子裝置之製造方法，其具有以下步驟： (a)於基材上塗佈聚醯亞胺前驅體組合物，上述聚醯亞胺前驅體組合物含有聚醯亞胺前驅體、具有P(=O)OH結構或P(=O)OR(式中，R為碳數4以上之烷基)結構之磷化合物及溶劑； (b)於上述基材上對上述聚醯亞胺前驅體進行加熱處理，製造於上述基材上積層有聚醯亞胺膜之積層體； (c)於上述積層體之聚醯亞胺膜上形成選自導電體層及半導體層之至少一層；及 (d)藉由外力將上述基材及上述聚醯亞胺膜進行剝離。 12.如上述第11項所記載之製造方法，其特徵在於：上述聚醯亞胺前驅體組合物係如上述第1至10項中任一項所記載之聚醯亞胺前驅體組合物。 13.如上述第11或12項所記載之製造方法，其中上述基材為玻璃板。 14.如上述第11至13中項任一項所記載之製造方法，其特徵在於，於剝離上述基材與上述聚醯亞胺膜之步驟中不進行雷射照射。 15.一種降低積層體之剝離強度之方法，其特徵在於：其係使積層體之基材與聚醯亞胺膜之間之剝離強度降低之方法，上述積層體具有上述基材及形成於該基材之聚醯亞胺膜，且 用以形成上述聚醯亞胺膜之聚醯亞胺前驅體組合物含有具有P(=O)OH結構或P(=O)OR(式中，R為碳數4以上之烷基)結構之磷化合物。 16.如上述第15項所記載之方法，其特徵在於：上述聚醯亞胺前驅體組合物為如上述第1至10中任一項所記載之聚醯亞胺前驅體組合物。 17.如上述第15或16項所記載之方法，其中上述基材為玻璃板。 [發明之效果][化1]

(In the general formula (I), X ₁ is a tetravalent aliphatic or aromatic group, Y ₁ is a divalent aliphatic or aromatic group, and R ₁ and R ₂ are independently hydrogen atoms and carbon numbers 1 to 6 alkyl group or carbon number 3 to 9 alkylsilyl group) 6. The composition as described in item 5 above, characterized in that: relative to the total repeating units, X ₁ is 4 having an alicyclic structure The content of the repeating unit represented by the general formula (I) in which _{Y 1} is a divalent group having an alicyclic structure is 50 mol% or less. 7. The composition as described in the above item 5, characterized in that X ₁ in the general formula (I) is a tetravalent group _{having an aromatic ring, and Y 1} is a divalent group having an aromatic ring. 8. The composition as described in item 5 above, wherein X ₁ in the general formula (I) is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. 9. The composition as described in item 5 above, wherein X ₁ in the general formula (I) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure. 10. The composition according to the above item 5, wherein: a ratio of the total repeating units containing more than 60% of X formula (I) having the repeating unit ₁ based tetravalent aliphatic ring structure of the group ( However, relative to the total repeating units, the content of the repeating unit represented by the general formula (I) in _{which X 1} is a tetravalent group with an alicyclic structure and Y _{1 is a divalent group with an alicyclic structure is 50 mol% or less} ). 11. A method for manufacturing a flexible electronic device, which has the following steps: (a) Coating a polyimide precursor composition on a substrate, the polyimide precursor composition containing a polyimine precursor P(=O)OH structure or P(=O)OR (wherein R is an alkyl group with 4 or more carbons) structure and a solvent; The imine precursor is heated to produce a laminate with a polyimide film laminated on the substrate; (c) forming at least one layer selected from a conductive layer and a semiconductor layer on the polyimide film of the laminate And (d) peeling off the above-mentioned base material and the above-mentioned polyimide film by external force. 12. The production method according to item 11 above, wherein the polyimide precursor composition is the polyimide precursor composition described in any one of items 1 to 10 above. 13. The manufacturing method according to the above item 11 or 12, wherein the substrate is a glass plate. 14. The manufacturing method according to any one of items 11 to 13, characterized in that no laser irradiation is performed in the step of peeling the base material and the polyimide film. 15. A method for reducing the peel strength of a laminate, characterized in that it is a method of reducing the peel strength between the base material of the laminate and the polyimide film, the laminate having the base material and being formed on the base material. The polyimide film of the base material, and the polyimide precursor composition used to form the above-mentioned polyimide film contains a P(=O)OH structure or P(=O)OR (where R is Phosphorus compounds with a carbon number of 4 or more alkyl) structure. 16. The method according to item 15 above, wherein the polyimide precursor composition is the polyimide precursor composition as described in any one of 1 to 10 above. 17. The method according to the above item 15 or 16, wherein the substrate is a glass plate. [Effects of Invention]

According to the present invention, it is possible to provide a polyimide precursor composition that can manufacture flexible electronic devices by industrially simple devices and steps. Furthermore, according to the present invention, it is possible to provide a simple and convenient manufacturing method for a flexible electronic device using a polyimide film as a substrate. If the polyimide precursor composition of the present invention is used, the peel strength between the substrate and the polyimide film can be appropriately reduced. Therefore, the flexible electronic device can be manufactured by simple devices and steps, and the risk of damage to the components during the manufacturing process is small and the yield rate is high.

In this application, "flexible (electronic) device" means that the device itself has flexibility. Generally, a semiconductor layer (transistor, diode, etc. as a component) is formed on a substrate to complete the device. The "flexible (electronic) device" is different from the previous FPC (Flexible Print Circuit, flexible printed wiring board) mounted with "hard" semiconductor components such as IC chips, such as COF (Chip On Film, flip chip film), etc. Device. However, in order to operate or control the "flexible (electronic) device" in this case, it is entirely possible to mount or electrically connect "hard" semiconductor components such as IC chips on a flexible substrate for fusion and use. . As flexible (electronic) devices that are preferably used, display devices such as liquid crystal displays, organic EL displays, and electronic paper, solar cells, and light receiving devices such as CMOS (Complementary Metal Oxide Semiconductor) can be cited.

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

＜＜Polyimine precursor composition＞＞ The polyimide precursor composition used to form the polyimide film contains a polyimide precursor, a phosphorus compound and a solvent. Both the polyimide precursor and the phosphorus compound are dissolved in the solvent. In this application, the term "polyimide precursor" when used means the polyimide precursor that can form the polyimide film. That is, the term "polyimide precursor" includes polyimide acid and its derivatives (see formula (I) for precise definition), partially imidized polyimide polyimide acid and derivatives, And polyimide, but both are soluble in solvents.

The polyimide precursor has a repeating unit represented by the following general formula (I):

(通式(I)中，X₁ 係4價之脂肪族基或芳香族基，Y₁ 係2價之脂肪族基或芳香族基，R₁ 及R₂ 相互獨立地為氫原子、碳數1～6之烷基或碳數3～9之烷基矽烷基)。 尤佳為R₁ 及R₂ 係氫原子之聚醯胺酸。[化2]

(In the general formula (I), X ₁ is a tetravalent aliphatic or aromatic group, Y ₁ is a divalent aliphatic or aromatic group, and R ₁ and R ₂ are independently hydrogen atoms and carbon numbers 1-6 alkyl group or C3-9 alkylsilyl group). Particularly preferred is polyamide acid in which _{R 1} and R _{2 are hydrogen atoms.}

In addition, the polyimidized polyimide precursor contains at least one repeating unit of the two amide structures in the general formula (I).

The polyimide formed from the polyimide precursor having the repeating unit represented by the general formula (I) has the repeating unit represented by the following general formula (II):

(式中，X₁ 係4價之脂肪族基或芳香族基，Y₁ 係2價之脂肪族基或芳香族基)。 於聚醯亞胺可溶解之情形時，可作為「聚醯亞胺前驅體」包含於聚醯亞胺前驅體組合物中。[化3]

(In the formula, X ₁ is a tetravalent aliphatic or aromatic group, and Y ₁ is a divalent aliphatic or aromatic group). When the polyimide is soluble, it can be included in the polyimide precursor composition as a "polyimine precursor".

_{Hereinafter, the structure of X 1} and Y _{2 in} the above repeating units (general formulas (I) and (II)) and the monomers (tetracarboxylic acid component, diamine component, and other components) used for the production The chemical structure of polyimide is explained, and then the manufacturing method is explained.

In this specification, the tetracarboxylic acid component includes tetracarboxylic acid derived from tetracarboxylic acid, tetracarboxylic dianhydride, other tetracarboxylic silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chloride, which are used as raw materials for the production of polyimine. Things. It is relatively simple to use tetracarboxylic dianhydride in production. In the following description, an example of using tetracarboxylic dianhydride as a tetracarboxylic acid component will be described, but it is not particularly limited. In addition, the diamine component is a diamine compound _{containing two amine groups (-NH 2} ) used as a raw material for the production of polyimine.

In addition, in this specification, the meaning of the polyimide film includes both the film formed on the (carrier) substrate and existing in the laminate, and the film after the substrate is peeled off. In addition, the material constituting the polyimide film, that is, the material obtained by heat-treating (imidizing) the polyimide precursor composition is sometimes referred to as "polyimide material".

The polyimine contained in the polyimide film is not limited, and includes polyimine in which a tetracarboxylic acid component and a diamine component are appropriately selected from aromatic compounds and aliphatic compounds. The aliphatic compound of the diamine component is preferably an alicyclic compound. Examples of polyimines include wholly aromatic polyimines, semialicyclic polyimines, and fully alicyclic polyimines.

In order to make the obtained polyimide material excellent in heat resistance, it is preferable that X ₁ in the general formula (I) is a tetravalent group _{having an aromatic ring, and Y 1} is a divalent group having an aromatic ring, but there is no Specially limited. In addition, in order to make the obtained polyimide material excellent in heat resistance and transparency, it is preferable that X ₁ is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. In addition, in order for the obtained polyimide material to have excellent heat resistance and dimensional stability, it is preferable that X ₁ is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure.

With regard to the properties of the obtained polyimide material, such as transparency, mechanical properties, or heat resistance, it is preferable that X ₁ is a tetravalent group with an alicyclic structure, and Y ₁ is a tetravalent group with an alicyclic structure relative to the total repeating unit. The content of the repeating unit represented by the formula (I) of the divalent group of the alicyclic structure is preferably 50 mol% or less, more preferably 30 mol% or less or less than 30 mol%, more preferably 10 mol% %the following.

In one embodiment, it is preferable that X ₁ is a tetravalent group _{having an aromatic ring, and Y 1} is a divalent group having an aromatic ring, one of the repeating units of the above formula (I) relative to the total repeating units. The total content of the above is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%. In this embodiment, when a polyimide material with particularly high transparency is required, it is preferable that the polyimide contains a fluorine atom. That is, it is preferable that the polyimide contains _{the repeating unit of the general formula (I) with X 1} having a tetravalent group containing an aromatic ring-containing fluorine atom and/or Y ₁ having a fluorine atom containing an aromatic ring. One or more of the repeating units of the above-mentioned general formula (I) as a divalent group.

In one embodiment, the polyimide is preferably _one of the above-mentioned general formula (I) in _{which X 1} is a tetravalent group having an alicyclic structure, and Y 1 is a divalent group having an aromatic ring, relative to the total repeating units. The total content of one or more repeating units is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%.

In one embodiment, the polyimide is preferably a repeat of the above formula (I) in _{which X 1} is a tetravalent group having an aromatic ring, and Y _{1 is a divalent group having an alicyclic structure, relative to the total repeating units.} The total content of one or more of the units is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 Mol%.

<Tetracarboxylic acid component and X _1> X ₁ is the aromatic ring group having a valence of 4, preferably 6 to 40 carbon atoms having a tetravalent group of the aromatic ring.

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

(式中，Z₁ 為直接鍵、或下述2價基之任一者：[化4]

(In the formula, Z ₁ is a direct bond or any of the following divalent groups:

其中，式中之Z₂ 係2價之有機基，Z₃ 、Z₄ 分別獨立地為醯胺鍵、酯鍵、羰基鍵，Z₅ 係包含芳香環之有機基)[化5]

_{Among them, Z 2} in the formula is a divalent organic group, Z ₃ and Z ₄ are independently an amide bond, an ester bond, and a carbonyl bond, respectively, and Z ₅ is an organic group containing an aromatic ring)

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

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

As the tetravalent group having an aromatic ring, the following are particularly preferred because the obtained polyimide film can have both high heat resistance and high transparency.

(式中，Z₁ 為直接鍵、或六氟亞異丙基鍵)[化6]

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

Here, Z _{1 is more} preferably a direct bond, so that the obtained polyimide film can have high heat resistance, high transparency, and low linear thermal expansion coefficient.

In addition, as a preferable base, a compound in which Z ₁ in the above formula (9) is a lanyl group-containing group represented by the following formula (3A) can be cited:

Z₁₁ 及Z₁₂ 分別獨立地較佳為相同，係單鍵或2價之有機基。作為Z₁₁ 及Z₁₂ ，較佳為包含芳香環之有機基，例如較佳為式(3A1)所示之結構：[化7]

Z ₁₁ and Z ₁₂ are each independently preferably the same, and are a single bond or a divalent organic group. As Z ₁₁ and Z ₁₂ , it is preferably an organic group containing an aromatic ring, for example, a structure represented by formula (3A1):

(Z₁₃ 及Z₁₄ 相互獨立地為單鍵、-COO-、-OCO-或-O-，此處，於Z₁₄ 鍵結於茀基之情形時，較佳為Z₁₃ 為-COO-、-OCO-或-O-、Z₁₄ 為單鍵之結構；R₉₁ 為碳數1～4之烷基或苯基，較佳為甲基，n為0～4之整數，較佳為1)。[化8]

(Z ₁₃ and Z ₁₄ are independently a single bond, -COO-, -OCO-, or -O-. Here, when Z _{14 is} bonded to a green group, it is preferable that Z ₁₃ is -COO-, -OCO- or -O-, Z ₁₄ is a single bond structure; R ₉₁ is an alkyl group or phenyl group with 1 to 4 carbon atoms, preferably a methyl group, n is an integer of 0 to 4, preferably 1) .

As the tetracarboxylic acid component that provides the repeating unit of the general formula (I) with a tetravalent group of _{X 1 having an aromatic ring, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane,} 4-(2,5-di-oxotetrahydrofuran-3-yl)-1,2,3,4-tetralin-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 Dicarboxylic acid, bis(3,4-dicarboxyphenyl), m-triphenyl-3,4,3',4'-tetracarboxylic acid, p-triphenyl-3,4,3',4' -Tetracarboxylic acid, biscarboxyphenyl dimethyl silane, bis dicarboxyphenoxy diphenyl sulfide, sulfonyl diphthalic acid, and these tetracarboxylic dianhydrides, tetracarboxylic silane esters, tetracarboxylic acid Derivatives of acid esters, tetracarboxylic acid chloride, etc. As the tetracarboxylic acid component that provides X ₁ is a repeating unit of the general formula (I) having a tetravalent group containing an aromatic ring fluorine atom, for example, 2,2-bis(3,4-dicarboxyphenyl) can be cited Hexafluoropropane, and derivatives of these tetracarboxylic dianhydrides, tetracarboxylic silyl esters, tetracarboxylic esters, and tetracarboxylic acid chlorides. Furthermore, as a preferable compound, (9H-茀-9,9-diyl)bis(2-methyl-4,1-phenylene)bis(1,3-dioxo-1,3- Dihydroisobenzofuran-5-carboxylate). The tetracarboxylic acid component may be used singly, or plural kinds may be used in combination.

The _{tetravalent group having an alicyclic structure of X 1} is preferably a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms, more preferably having at least one aliphatic ring having 4 to 12 members, more preferably an aliphatic group 4-membered ring or aliphatic 6-membered ring. As a tetravalent group having a preferable aliphatic 4-membered ring or aliphatic 6-membered ring, the following can be cited.

(式中，R₃₁ ～R₃₈ 分別獨立地為直接鍵、或2價之有機基。R₄₁ ～R₄₇ 分別獨立地表示選自由式：-CH₂ -、-CH=CH-、-CH₂ CH₂ -、-O-、-S-所示之基所組成之群中的1種。R₄₈ 係包含芳香環或脂環結構之有機基)[化9]

(In the formula, R ₃₁ to R ₃₈ are each independently a direct bond or a divalent organic group. R ₄₁ to R ₄₇ each independently represent a free _{formula: -CH 2} -, -CH=CH-, -CH ₂ One of the group consisting of groups represented by _{CH 2 -, -O-, -S-. R 48} is an organic group containing an aromatic ring or an alicyclic structure)

Specific examples of R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , and R ₃₈ include direct bonds, or aliphatic hydrocarbon groups with 1 to 6 carbon atoms, or oxygen atoms (-O-) , Sulfur atom (-S-), carbonyl bond, ester bond, amide bond.

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

(式中，W₁ 係直接鍵或2價之有機基，n₁₁ ～n₁₃ 分別獨立地表示0～4之整數，R₅₁ 、R₅₂ 、R₅₃ 分別獨立地為碳數1～6之烷基、鹵基、羥基、羧基、或三氟甲基)[化10]

(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 each independently an alkane with 1 to 6 carbon atoms Group, halo, hydroxy, carboxy, or trifluoromethyl)

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

(式(6)中之R₆₁ ～R₆₈ 分別獨立地表示直接鍵或上述式(5)所示之2價基之任一者)[化11]

_{(R 61} to R ₆₈ in the formula (6) each independently represent any one of a direct bond or the divalent group shown in the above formula (5))

As the tetravalent group having an alicyclic structure, the following is particularly preferred, because it allows the obtained polyimide to have both high heat resistance, high transparency, and low linear thermal expansion coefficient.

[化12]

As the tetracarboxylic acid component to provide lines with X ₁ of formula (I) 4 ring structure of divalent aliphatic group of repeating units, for example, 1,2,3,4-cyclobutane tetracarboxylic acid, isopropylidene two Phenoxy diphthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bis(cyclohexane)]-3,3',4,4'-tetra Carboxylic acid, [1,1'-bis(cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-bis(cyclohexane)]-2,2', 3,3'-tetracarboxylic acid, 4,4'-methylene bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl) bis(cyclo Hexane-1,2-dicarboxylic acid), 4,4'-oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis(cyclohexane-1,2 -Dicarboxylic acid), 4,4'-sulfonyl bis(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), octahydrocyclopentadiene-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]oct-5-ene-2,3,7,8-tetracarboxylic acid , Tricyclo[4.2.2.02,5]decane-3,4,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]dec-7-ene-3,4,9,10-tetracarboxylic acid Acid, 9-oxatricyclo[4.2.1.02,5]nonane-3,4,7,8-tetracarboxylic acid, norran-2-spiro-α-cyclopentanone-α'-spiro-2 ''-Norethane 5,5'',6,6''-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethynaphthalene-2c,3c,6c, 7c-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethynaphthalene-2t,3t,6c,7c-tetracarboxylic acid, and these tetracarboxylic dianhydrides, Derivatives of tetracarboxylic acid silyl ester, tetracarboxylic acid ester, tetracarboxylic acid chloride, etc. The tetracarboxylic acid component may be used singly, or plural kinds may be used in combination.

<Y ₁ and diamine component> The _{divalent group having an aromatic ring of Y 1} is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms, and more preferably having 6 to 20 carbon atoms .

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

(式中，W₁ 係直接鍵、或2價之有機基，n₁₁ ～n₁₃ 分別獨立地表示0～4之整數，R₅₁ 、R₅₂ 、R₅₃ 分別獨立地碳數1～6之烷基、鹵基、羥基、羧基、或三氟甲基)[化13]

(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 each independently an alkane having 1 to 6 carbon atoms Group, halo, hydroxy, carboxy, or trifluoromethyl)

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

[化14]

(式(6)中之R₆₁ ～R₆₈ 分別獨立地表示直接鍵或上述式(5)所示之2價基之任一者)[化15]

_{(R 61} to R ₆₈ in the formula (6) each independently represent any one of a direct bond or the divalent group shown in the above formula (5))

Here, in order for the obtained polyimide to have both high heat resistance, high transparency, and low linear thermal expansion coefficient, W _{1 is} particularly preferably a direct bond or selected from the formula: -NHCO-, -CONH-,- One of the groups consisting of the groups shown by COO- and -OCO-. In addition, W _{1 is} also particularly preferably that R ₆₁ to R ₆₈ are direct bonds, or one selected from the group consisting of groups represented by -NHCO-, -CONH-, -COO-, -OCO- Any one of the divalent groups represented by the above formula (6).

In addition, as a preferred base, a compound in the above formula (4) where W ₁ is a phosphonium-containing group represented by the following formula (3B) can be cited:

Z₁₁ 及Z₁₂ 分別獨立地較佳為相同，為單鍵或2價之有機基。作為Z₁₁ 及Z₁₂ ，較佳為包含芳香環之有機基，較佳為例如式(3B1)所示之結構：[化16]

Z ₁₁ and Z ₁₂ are each independently preferably the same, and are a single bond or a divalent organic group. As Z ₁₁ and Z ₁₂ , it is preferably an organic group containing an aromatic ring, preferably a structure represented by formula (3B1):

(Z₁₃ 及Z₁₄ 相互獨立地為單鍵、-COO-、-OCO-或-O-，此處，於Z₁₄ 鍵結於茀基之情形時，較佳為Z₁₃ 為-COO-、-OCO-或-O-、Z₁₄ 為單鍵之結構；R₉₁ 為碳數1～4之烷基或苯基，較佳為苯基，n為0～4之整數，較佳為1)。[化17]

(Z ₁₃ and Z ₁₄ are independently a single bond, -COO-, -OCO-, or -O-. Here, when Z _{14 is} bonded to a green group, it is preferable that Z ₁₃ is -COO-, -OCO- or -O-, Z ₁₄ is a single bond structure; R ₉₁ is an alkyl group with 1 to 4 carbons or a phenyl group, preferably a phenyl group, n is an integer of 0 to 4, preferably 1) .

As another preferable group, a compound in which W ₁ is a phenylene diamine compound in the above formula (4), namely, a terphenylenediamine compound, is particularly preferable, a compound in which all are para-bonds.

As another preferable group, in the above formula (4), W _{1 is a compound in which R 61} and R ₆₂ are 2,2-propylene groups in the structure of the first phenyl ring of formula (6).

As another preferred base, a compound represented by the following formula (3B2) in _{W 1 in the above formula (4) can be cited:}

。[化18]

.

As the diamine component that provides the repeating unit of the general formula (I) with a divalent group having an aromatic ring as Y _{1, for example, p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino group} -Biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, m-tolidine, 4,4'-diaminobenzidine Aniline, 3,4'-diaminobenzamidine, N,N'-bis(4-aminophenyl)p-xylylenedimethamide, N,N'-p-phenylene bis(p-amino Benzamide), 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'-oxydiphenylamine, 3,4'-oxy Diphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzene) Oxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-amino) Phenoxy) biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis( 4-aminophenyl) sulfide, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-bis((aminophenoxy)phenyl)propane, 2,2'-bis( 3-Amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl) bis(4-(3-aminophenoxy)diphenyl) ) Sulfur, 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)-6-ethylamino-1,3, 5-triazine, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-triazine. As Y ₁ is the diamine component of the repeating unit of general formula (I) having a divalent group containing a fluorine atom in an aromatic ring, for example, 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. In addition, as a preferred diamine compound, 4,4'-(((9H-茀-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'-binaphthyl ]-2,2'-Diylbis(oxy))diamine. The diamine component may be used alone, or plural kinds may be used in combination.

The _{divalent group having an alicyclic structure of Y 1} is preferably a divalent group having an alicyclic structure with 4 to 40 carbon atoms, and more preferably has at least one aliphatic ring with 4 to 12 members, more preferably aliphatic The 6-member ring of the clan.

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

(式中，V₁ 、V₂ 分別獨立地為直接鍵或2價之有機基，n₂₁ ～n₂₆ 分別獨立地表示0～4之整數，R₈₁ ～R₈₆ 分別獨立地為碳數1～6之烷基、鹵基、羥基、羧基或三氟甲基，R₉₁ 、R₉₂ 、R₉₃ 分別獨立地為選自式：-CH₂ -、-CH=CH-、-CH₂ CH₂ -、-O-、-S-所示之基所組成之群中之1種)[化19]

(In the formula, V ₁ and V ₂ are each independently a direct bond or a divalent organic group, n ₂₁ to n ₂₆ each independently represent an integer of 0 to 4, and R ₈₁ to R ₈₆ each independently represent a carbon number of 1 to Alkyl group, halo group, hydroxyl group, carboxyl group or trifluoromethyl group of 6, R ₉₁ , R ₉₂ , and R ₉₃ are each independently selected from the formula: -CH ₂ -, -CH=CH-, -CH ₂ CH _2- , -O-, -S- as shown in the group consisting of one of the groups)

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

As the divalent group having an alicyclic structure, in order for the obtained polyimide to have both high heat resistance and low linear thermal expansion coefficient, the following is particularly preferred.

作為具有脂環結構之2價基，其中，較佳為下述者。[化20]

The divalent group having an alicyclic structure is preferably the following.

[化21]

As the diamine component that imparts Y _{1 to} the repeating unit of the general formula (I) having a divalent group having an alicyclic structure, for example, 1,4-diaminocyclohexane, 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 -Second butyl cyclohexane, 1,4-diamino-2-tertiary butyl cyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane, 1 ,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxy Bicycloheptane, diaminomethyloxybicycloheptane, isophorone diamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, bis( Aminocyclohexyl) isopropylidene, 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindene, 6 ,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindene. The diamine component may be used alone, or plural kinds may be used in combination.

In a preferred embodiment of the invention of the polyimide precursor, the polyimide precursor is not only composed of 3,3',4,4'-biphenyltetracarboxylic acid derivatives (dianhydrides) and p-benzene Polyimine precursor derived from diamine. _{Preferably, X 1} of general formula (I) is derived from 3,3',4,4'-biphenyltetracarboxylic acid derivatives (s-BPDA, etc.), and Y _{1 is} derived from one of the repeating units of p-phenylenediamine (PPD) The ratio is 25 mol% or less of the total repeating units, more preferably 10 mol% or less, and also preferably 0 mol% (not including at least one of s-BPDA and the like and PPD).

In a preferred embodiment of the invention of the polyimide precursor, the polyimide precursor and the polyimine are not exclusively composed of tetracarboxylic acid derivatives (dianhydrides) with aromatic rings and no fluorine atoms. Polyimine precursor and polyimide obtained with a diamine compound having an aromatic ring and no fluorine atom. That is, it is preferable that _{at least one of X 1} and Y ₁ of the general formula (I) includes a repeating unit having an alicyclic structure or an aromatic ring containing a fluorine atom. Preferably, in the total repeating units, X ₁ of the general formula (I) is a repeating unit having an aromatic ring group (except for those containing fluorine) and Y ₁ is a repeating unit having an aromatic ring group (except for those containing fluorine) The ratio is 25 mol% or less, more preferably 10 mol% or less, and also preferably 0 mol% ( _{at least one of X 1} and Y ₁ is a group that does not have an aromatic ring and does not contain a fluorine atom) .

As the tetracarboxylic acid component and diamine component that provide the repeating unit represented by the above general formula (I), aliphatic tetracarboxylic acids (especially dianhydrides) and/or aliphatic diamines other than alicyclic can be used Either one is preferably 100 mol% relative to the total of the tetracarboxylic acid component and the diamine component, and its content is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less , And more preferably 10 mol% or less (including 0%).

Among the above, a preferred embodiment of the present invention includes that _{the ratio of X 1} of the general formula (I) is a tetravalent group having an alicyclic structure and the ratio of repeating units exceeds 60% of the total repeating units, more preferably 70 mol% Above, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%. When the alicyclic structure is less than 100%, the remaining part is preferably a tetravalent group with an aromatic ring in _{X 1.} The preferred tetravalent group having an alicyclic structure and the tetravalent group having an aromatic ring are as described above. In addition, Y ₁ may be any one of a divalent group having an aromatic ring and a divalent group having an alicyclic structure, and is preferably as described above. With respect to the total repeating units, X ₁ is 4 having an alicyclic structure The content of the repeating unit represented by formula (I) with a valence group and Y ₁ is a divalent group having an alicyclic structure is preferably 50 mol% or less, more preferably 30 mol% or less or less than 30 mol% , More preferably 10 mol% or less.

Furthermore, in another preferred embodiment of the present invention, polyimide (and polyimide material) having a breaking strength of 80 MPa or more when formed into a film is preferable. For the breaking strength, for example, a value obtained from a film having a film thickness of about 5 to 100 μm can be used. In addition, the breaking strength is the value obtained for the following film, which is obtained by heating the polyimide precursor solution composition or the coating film of the polyimide solution composition at a maximum temperature of 310°C .

The polyimide precursor can be produced from the above-mentioned tetracarboxylic acid component and diamine component. The polyimide precursor used in the present invention (the polyimide precursor containing at least one of the repeating units represented by the above formula (I)) can be classified into the chemical structure adopted _{by R 1} and R ₂ ： 1) Polyamide acid (R ₁ and R ₂ are hydrogen), 2) Polyamide acid ester ( _{At least a part of R 1} and R ₂ is an alkyl group), 3) 4) Polyamide silyl ester (R _{At least a part of 1} and R ₂ is an alkylsilyl group). Furthermore, according to this classification, each polyimide precursor can be easily manufactured by the following manufacturing method. However, the production method of the polyimide precursor used in the present invention is not limited to the following production methods.

1) Polyamide The polyimide precursor can be obtained in the form of a polyimide precursor solution by the following method: in a solvent, the tetracarboxylic dianhydride and the diamine component, which are the tetracarboxylic acid components, are approximately equal molar , Preferably, the molar ratio of the diamine component to the tetracarboxylic acid component [the molar ratio of the diamine component/the molar number of the tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05 For example, at a relatively low temperature below 120°C, the reaction is carried out while suppressing the imidization.

More specifically, the diamine is dissolved in an organic solvent or water, the tetracarboxylic dianhydride is slowly added while stirring the solution, and stirring is carried out in the range of 0 to 120°C, preferably 5 to 80°C for 1 to 72 hours, Thereby, a polyimide precursor can be obtained, but it is not limited to this. In the case of the reaction above 80°C, the molecular weight will vary according to the temperature history during polymerization, and heat will cause the imidization to proceed, so there is a possibility that the polyimide precursor cannot be produced stably. The order of addition of the diamine and the tetracarboxylic dianhydride in the above-mentioned production method tends to increase the molecular weight of the polyimide precursor, which is preferable. In addition, the order of addition of diamine and tetracarboxylic dianhydride in the above-mentioned production method can be reversed, since this can reduce precipitates, which is preferable. In the case of using water as a solvent, it is preferable to add 1,2-dimethylimidazole and the like in an amount of 0.8 times equivalent or more with respect to the carboxyl group of the produced polyimide acid (polyimide precursor) Bases such as imidazoles or triethylamine.

2) Polyurethane After reacting tetracarboxylic dianhydride with any alcohol to obtain diester dicarboxylic acid, it is reacted with a chlorinating reagent (thionine chloride, oxalic chloride, etc.) to obtain diester dicarboxylic acid chloride. The diester dicarboxylic acid chloride and diamine are stirred at -20 to 120°C, preferably -5 to 80°C for 1 to 72 hours, thereby obtaining a polyimide precursor. In the case of the reaction above 80°C, the molecular weight will vary according to the temperature history during polymerization, and heat will cause the imidization to proceed, so there is a possibility that the polyimide precursor cannot be produced stably. In addition, by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, etc., a polyimide precursor can also be easily obtained.

The polyimide precursor obtained by this method is stable, so solvents such as water or alcohol can also be added for purification such as reprecipitation.

3) Polysilyl amide (indirect method) The diamine is reacted with the silylation agent in advance to obtain the silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, dissolve the silylated diamine in the dehydrated solvent, slowly add tetracarboxylic dianhydride while stirring, and stir for 1 to 72 hours in the range of 0 to 120°C, preferably 5 to 80°C. This obtains a polyimide precursor. In the case of the reaction above 80°C, the molecular weight will vary according to the temperature history during polymerization, and heat will cause the imidization to proceed, so there is a possibility that the polyimide precursor cannot be produced stably.

4) Polysilyl amide (direct method) The polyimide solution obtained by the method of 1) is mixed with the silylation agent, and stirred at 0-120°C, preferably 5-80°C for 1 to 72 hours, thereby obtaining a polyimide precursor. In the case of the reaction above 80°C, the molecular weight will vary according to the temperature history during polymerization, and heat will cause the imidization to proceed, so there is a possibility that the polyimide precursor cannot be produced stably.

As the silylating agent used in the method of 3) and the method of 4), if a chlorine-free silylating agent is used, there is no need to purify the silylated polyamide acid or the obtained polyimide, so it is more good. As the silylation agent containing no chlorine atom, N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, hexamethylbis Silazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are especially preferred because they do not contain fluorine atoms and are low in cost.

In addition, in the silylation reaction of diamine in the method of 3), in order to promote the reaction, an amine catalyst such as pyridine, piperidine, and triethylamine can be used. The catalyst can be used directly as a polymerization catalyst for the precursor of polyimide.

The solvent used when preparing the polyimide precursor is preferably water, or, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone , N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfide and other aprotic solvents, as long as it can dissolve the monomer components of the raw materials and the resulting polyamide As the amine precursor, any kind of solvent can be used, so its structure is not particularly limited. As the solvent, water, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, etc. are preferably used. Amine solvents; cyclic ester solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc.; carbonic acid Carbonate solvents such as ethylene glycol and propylene carbonate; glycol solvents such as triethylene glycol; phenolic solvents such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol; acetophenone, 1 , 3-Dimethyl-2-imidazolidinone, cyclobutane, dimethyl sulfoxide, etc. Furthermore, other general organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl acetate can also be used. Cellosolve, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl Base ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha solvents, etc. . In addition, a plurality of solvents may be used in combination.

The logarithmic viscosity of the polyimide precursor is not particularly limited. Preferably, the logarithmic viscosity in the N,N-dimethylacetamide solution with a concentration of 0.5 g/dL at 30°C is 0.2 dL/g or more, more preferably It is 0.3 dL/g or more, particularly preferably 0.4 dL/g or more. If the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is higher, and the resulting polyimide has excellent mechanical strength and heat resistance.

As the polyimide precursor, a wide range of about 0% (less than 5%) to about 100% (above 95%) can be used as the imidization rate of the polyimide precursor. The polyimide precursors (polyamide acid, polyamide acid ester, polyamide silyl ester) obtained by the above method have a low imidization rate. Carry out the imidization treatment (thermal imidization, chemical imidization) on these in the solution, so that the imidization progresses and can be adjusted to the desired imidization rate. For example, by stirring the polyamide acid solution in the range of, for example, 80 to 230°C, preferably 120 to 200°C, for example, 1 to 24 hours, a polyimide precursor that undergoes imidization can be obtained. When the polyimine is soluble in a solvent, the following polyimine can also be dissolved in the solvent to be used as a polyimide precursor for film formation. The polyimide is the imidization reaction of the polyimide The latter reaction mixture is poured into a poor solvent to precipitate polyimine, or a solution of polyimine precursor (low imidization rate) (if necessary, containing imidization catalyst and dehydrating agent) ) For example, it is obtained by casting on a carrier substrate, heat-treating and drying, thereby performing imidization (thermal imidization, chemical imidization).

＜Phosphorus compounds＞ The phosphorus compound that can be used is a compound having at least one structure selected from P(=O)OH and P(=O)OR (wherein R is an alkyl group with 4 or more carbons) in the molecule. The phosphorus compound preferably does not have an aryl group directly bonded to the phosphorus atom P, and more preferably does not contain an aryl group in the molecule. The phosphorus compound may have one or more phosphorus atoms in the molecule.

In a preferred embodiment of the present invention, the phosphorus compound contains only one phosphorus atom. As the compound containing one phosphorus atom, a compound represented by formula (P) can be cited.

式中，R₁ ～R₃ 之至少1個之基表示OH或碳數4以上之烷氧基，其餘基獨立地表示選自OH、烷氧基、H及烷基之基。[化22]

In the formula, _{at least one group of R 1} to R ₃ represents OH or an alkoxy group having a carbon number of 4 or more, and the remaining groups independently represent a group selected from OH, alkoxy, H and alkyl.

As the alkoxy group having 4 or more carbon atoms, preferably an alkoxy group having 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. These may be linear, branched, and alicyclic, and are preferably linear alkoxy. The alkoxy group having "the carbon number is not limited to 4 or more" includes preferably an alkoxy group having 1 to 18 carbon atoms. In addition to the above-mentioned alkoxy group having 4 or more carbon atoms, it may also include 1 to 3 carbon atoms.的alkoxy。

Examples of the alkyl group include an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. These may be linear, branched, or alicyclic, and are preferably linear alkyl.

When at _{least one of R 1} to R ₃ is OH, the remaining groups are not particularly limited, and are preferably selected from OH, alkoxy and alkyl. _{As the combination of R 1} to R _{3 in} this case, it can be enumerated that all are OH (phosphoric acid), 2 OH and 1 alkoxy (monoalkyl phosphate), 1 OH and 2 alkoxy (phosphoric acid) Dialkyl ester), 2 OH and 1 alkyl (monoalkyl phosphonic acid), 1 OH and 2 alkyl (dialkyl phosphinic acid), 1 OH, 1 alkoxy, 1 An alkyl group (monoalkyl phosphinic acid alkyl ester).

When at _{least one of R 1} to R ₃ is an alkoxy group with 4 or more carbon atoms, the remaining groups are not particularly limited, and are preferably selected from OH, alkoxy and alkyl groups. The case where OH is included as R ₁ to R ₃ corresponds to the case where the carbon number of the alkoxy group in the above combination is 4 or more. _{As a combination of R 1} to R ₃ selected from alkoxy and alkyl groups, all are alkoxy groups having 4 or more carbons (trialkyl phosphate), 2 alkoxy groups having 4 or more carbons, and 1 One alkyl group (monoalkyl phosphonic acid dialkyl ester), one alkoxy group with 4 or more carbon atoms, and two alkyl groups (monoalkyl dialkyl phosphinic acid ester). When the phosphorus compound contains a plurality of alkoxy groups, in order to facilitate the acquisition, these are preferably the same. Therefore, when it is necessary to include an "alkoxy group with 4 or more carbons" in the compound, the plural alkoxy groups are preferably the same "alkoxy group with 4 or more carbons".

Examples of the phosphorus compound having a plurality of phosphorus atoms include polyphosphoric acid such as diphosphoric acid, triphosphoric acid, cyclotriphosphoric acid, and tetraphosphoric acid, and ester compounds (partially or wholly esterified compounds) thereof. In the case of a fully esterified compound, at least a part, preferably all of the alkoxy moiety of the ester is an alkoxy group having 4 or more carbon atoms. In the case of a partially esterified compound, the carbon number of the alkoxy moiety is not limited, and it is preferably an alkoxy group with 4 or more carbon atoms.

As the phosphorus compound containing a plurality of phosphorus atoms, compounds having a poly or oligophosphate structure can also be cited. Specifically, the compound represented by the general formula (PPE) can be cited.

[化23]

In the formula (PPE), R ₁ to R ₃ each independently, and plural R ₂ also each independently represent a group selected from OH, alkoxy, H and alkyl, and at least one _{group of R 1} to R ₃ Represents OH or an alkoxy group with 4 or more carbon atoms. R ₄ represents a divalent hydrocarbon group. n is an integer of 0 or more.

Same as R R ₁ ~ R ₃ is preferably of the group of formula (P) as shown in the ₁ ~ R _3. Most preferably, all of R ₁ to R ₃ represent an alkoxy group having 4 or more carbon atoms. R _{4 is} preferably a hydrocarbon group having 1 to 16 carbon atoms or less, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and preferably a linear or branched alkylene group. n is preferably 0-4, more preferably 0-2, and still more preferably 0.

In the present invention, there are cases where the molecular weight of the phosphorus compound is preferably less than 400, especially the phosphorus compound represented by formula (P) and the phosphorus compound represented by formula (PPE) preferably have a molecular weight less than 400.

As specific examples of phosphorus compounds, for example, phosphoric acid, methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, sec-butylphosphonic acid, isobutyl Phosphonic acid, tertiary butyl phosphonic acid, n-pentyl phosphonic acid, isopentyl phosphonic acid, neopentyl phosphonic acid, n-hexyl phosphonic acid, cyclohexyl phosphonic acid, heptyl phosphonic acid, n-octyl phosphonic acid, nonyl Phosphonic acid, decyl phosphonic acid, dodecyl phosphonic acid, dodecyl phosphonic acid, phenyl phosphonic acid, (4-hydroxyphenyl) phosphonic acid, methylene diphosphonic acid, 1,2-ethylene Diphosphonic acid, o-xylylene diphosphonic acid, m-xylylene diphosphonic acid, p-xylylene diphosphonic acid, dimethyl phosphinic acid, ethyl methyl phosphinic acid, diethyl Phosphinic acid, ethyl butyl phosphinic acid, dipropyl phosphinic acid, phenyl phosphinic acid, diphenyl phosphinic acid, methyl phenyl phosphinic acid, (2-carboxyethyl) phenyl phosphinic acid Phosphonic acid, (2-ethylhexyl) phosphonic acid mono-2-ethylhexyl, tri-n-butyl phosphate, tri-n-pentyl phosphate, tri-n-hexyl phosphate, tris(2-ethylhexyl) phosphate, phosphoric acid Tris(2-butoxyethyl) ester, tris(1H,1H,5H-octafluoropentyl) phosphate, 2-ethylhexyl diphenyl phosphate, dibutyl phosphite (= dibutyl phosphonate) ), diisobutyl phosphite (= diisobutyl phosphonate), etc. In the above compounds, the alkyl group can be substituted with structural isomers having the same carbon number, at least one H in the alkyl group or the aryl group can be substituted with fluorine, and the substitution position in the aryl group is arbitrary. Moreover, the phosphorus compound can be used individually or in combination of 2 or more types.

In one embodiment of the present invention, it is sometimes preferable that when the phosphorus compound is phosphoric acid or tributyl phosphate, the polyimine precursor composition and the polyimine precursor system are only composed of pyridine-2- Spiro-α-cyclopentanone-α'-spiro-2''-nor 𦯉ane-5,5'',6,6''-tetracarboxylic dianhydride (CpODA), 4,4'-diamino The composition of the polyimide precursors obtained from benzil aniline (DABAN) and p-phenylenediamine (PPD) is different. In one embodiment of the present invention, it is sometimes preferable that the polyimide precursor is selected from a combination of monomers different from the combination of CpODA, DABAN and PPD.

<The preparation of polyimide precursor composition> The polyimide precursor composition used in the present invention includes at least one polyimine precursor, at least one of the above-mentioned phosphorus compounds, and a solvent.

The peel strength between the polyimide film and the substrate can be considered to adjust the phosphorus compound content. Generally, if it is too small, the peeling strength is too high and peeling becomes difficult. On the other hand, if it is too much, it is not only wasted, but the peeling strength also becomes extremely small. In particular, the coloring of the colorless and transparent polyimide film becomes larger (yellowness b *Increase), there are situations in which it is not suitable for transparent use.

Relative to the total monomer units of the polyimide precursor (ie, the repeating units of formula (I) and formula (I) count as 2 mol), the content of the phosphorus compound is preferably more than 0.001 mol%, more preferably 0.005 mol% or more, more preferably 0.01 mol% or more, still more preferably 0.02 mol% or more, and still more preferably 0.05 mol% or more. In addition, it is usually less than 5 mol%, more preferably 4 mol% or less, still more preferably 3 mol% or less, and particularly preferably 2 mol% or less.

As the solvent, the solvent used in the preparation of the polyimide precursor described above can be used. Usually, the solvent used in the preparation of the polyimide precursor can be used directly, that is, the polyimide precursor solution can be used directly, or it can be used after dilution or concentration as needed. The phosphorus compound is dissolved in the polyimide precursor composition.

The viscosity (rotational viscosity) of the polyimide precursor of the present invention is not particularly limited. The rotational viscosity measured with an E-type rotary viscometer at a temperature of 25°C and a shear rate of 20 sec ^-1 is preferably 0.01 to 1000 Pa. sec, more preferably 0.1～100 Pa·sec. In addition, thixotropy can also be imparted as needed. The viscosity in the above range is easy to handle during coating and film formation, and shrinkage is suppressed, and the leveling property is excellent, so a good film can be obtained.

The polyimide precursor composition of the present invention may optionally contain chemical imidizing agents (anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), antioxidants, ultraviolet absorbers, and fillers (inorganic particles such as silica) Etc.), dyes, pigments, silane coupling agents and other coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), etc.

The preparation of the polyimide precursor composition can be prepared by adding and mixing a phosphorus compound or a solution of a phosphorus compound to the polyimide precursor solution obtained by the method described above. As long as it does not affect the reaction, the tetracarboxylic acid component and the diamine component may be reacted in the presence of a phosphorus compound.

＜＜Manufacturing of polyimide/substrate laminate and flexible electronic device＞＞ The manufacturing method of the flexible electronic device of the present invention has the following steps: (a) coating the polyimide precursor composition on a substrate; (b) applying the polyimide precursor composition on the substrate Heat treatment is performed to manufacture a laminate (polyimide/substrate laminate) with a polyimide film laminated on the above-mentioned substrate; (c) forming a polyimide film selected from conductive materials on the polyimide film of the above-mentioned laminate At least one of the bulk layer and the semiconductor layer; and (d) peeling off the base material and the polyimide film by external force.

The polyimide precursor composition that can be used in the method of the present invention contains a polyimide precursor, a phosphorus compound, and a solvent. As the phosphorus compound, those described in the item of the aforementioned phosphorus compound can be used. As the polyimine precursor, those described in the item of the polyimine precursor composition can be used. The preferred polyimine precursor described in the section of the polyimide precursor composition is also preferred in the method of the present invention, and is not particularly limited.

One embodiment of the method of the present invention does not include the following method: In step (a) of the method, the following precursor composition is used as a polyimide precursor composition, the precursor composition containing phosphoric acid or tributyl phosphate As the phosphorus compound, the tetracarboxylic acid component contains CpODA, the diamine component contains a mixture of DABAN and PPD, and in step (b), the polyimide/base is carried out under heating conditions of a maximum temperature of 410°C, preferably 410°C or higher. Manufacturing of laminated body. Preferably, it does not include the following method: In step (a), the method uses a precursor combination containing phosphoric acid or tributyl phosphate as a phosphorus compound, a tetracarboxylic acid component containing CpODA, and a diamine component containing a mixture of DABAN and PPD "Thickness" as a polyimide precursor composition.

First, in step (a), the polyimide precursor solution (including the high imidization rate of the imine solution, and, if necessary, the composition solution containing additives) is cast on the substrate, Heat treatment is used to carry out imidization and solvent removal (the polyimide solution is mainly used for solvent removal) to form a polyimide film, and a laminate of the substrate and the polyimide film (polyimide film) is obtained. Amine/base material laminate).

As the base material, heat-resistant materials are used, such as ceramic materials (glass, alumina, etc.), metal materials (iron, stainless steel, copper, aluminum, etc.), semiconductor materials (silicon, compound semiconductors, etc.) in plate or sheet form Film or sheet substrates such as substrates, or heat-resistant plastic materials (polyimide, etc.). Generally, it is preferably a flat and smooth plate shape, and glass substrates such as soda lime glass, borosilicate glass, alkali-free glass, sapphire glass, etc.; semiconductor (including compound semiconductor) substrates such as silicon, GaAs, InP, and GaN are usually used; iron , Stainless steel, copper, aluminum and other metal substrates. In particular, glass substrates have been developed to be flat, smooth and large-area, and easy to obtain, so they are preferred. The substrates may also be those with inorganic thin films (such as silicon oxide films) or resin thin films formed on the surface. The thickness of the plate-shaped substrate is not limited, and from the viewpoint of convenient handling, it is, for example, 20 μm to 4 mm, preferably 100 μm to 2 mm.

The method of casting the polyimide precursor solution onto the substrate is not particularly limited, and examples thereof include conventionally known methods such as spin coating, screen printing, bar coater, and electrodeposition.

In step (b), the polyimide precursor composition is heated on the substrate to convert it into a polyimide film to obtain a polyimide/substrate laminate. The conditions of the heat treatment are not particularly limited. For example, after drying in a temperature range of 50°C to 150°C, the highest heating temperature is, for example, 150°C to 600°C, preferably 200°C to 550°C, more preferably 250°C. The treatment is carried out at ℃～500℃. The heat treatment conditions when using the polyimide solution are not particularly limited. 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 or lower, More preferably, it is 450°C or lower.

The thickness of the polyimide film is preferably 1 μm or more, more preferably 2 μm or more, and still more preferably 5 μm or more. When the thickness is less than 1 μm, the polyimide film cannot maintain sufficient mechanical strength. For example, when used as a flexible electronic device substrate, it may not be able to withstand stress and be damaged. In addition, the thickness of the polyimide film is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less. If the thickness of the polyimide film becomes thicker, it may be difficult to realize the thinning of the flexible device. To maintain sufficient durability as a flexible device while further achieving thinning, the thickness of the polyimide film is preferably 2-50 μm.

In one embodiment, the polyimide film preferably has excellent optical properties such as 400 nm transmittance, total light transmittance (average transmittance at 380 nm to 780 nm), and yellowness b* (YI). When measuring on a 10 μm thick film, the light transmittance at 400 nm is preferably 50% or more, more preferably 70% or more, still more preferably 75% or more, most preferably 80% or more, and the total light transmittance is lower than It is preferably 84% or more, more preferably 85% or more, and the yellowness b*(YI) is preferably 0 or more and 5 or less, and more preferably 3 or less. Of the 400 nm transmittance, total light transmittance, and yellowness b*(YI), at least one is preferred, at least two are more preferred, and three are most satisfying at the same time.

In one embodiment, the polyimide film preferably has a small thickness direction retardation (retardation) R _th . In addition, in the polyimide precursor composition of the present invention, the addition of the phosphorus compound specified in the present invention hardly changes _{the R th of the obtained polyimide film.} Therefore, in the present invention, the peeling strength of the polyimide film and the substrate can be adjusted without affecting _{R th.}

The obtained polyimide film is closely laminated with a base material such as a glass substrate. In order to facilitate mechanical peeling, when measuring in accordance with JIS K6854-1, for example, in a tensile speed of 2 mm/min and a 90° peel test, the peel strength between the substrate and the polyimide film is preferably 0.8 N/in (N/25.4 mm) or less, more preferably 0.6 N/in or less, and still more preferably 0.4 N/in or less. On the other hand, the lower limit is preferably 0.01 N/in or more. The peel strength is usually measured in the air or in the atmosphere.

The polyimide film in the polyimide/substrate laminate may have a second layer such as a resin film or an inorganic film on the surface. That is, after forming the polyimide film on the substrate, the second layer may be laminated to form a flexible electronic device substrate. It is preferable to have an inorganic film at least, and it is especially preferable to function as a barrier layer for water vapor, oxygen (air), and the like. Examples of the water vapor barrier layer include those selected from silicon nitride (SiN _x ), silicon _{oxide (SiO x} ), silicon oxynitride (SiO _x N _y ), aluminum oxide (Al ₂ O ₃ ), and titanium oxide (TiO ₂ ) Inorganic films of inorganic substances in the group consisting of metal oxides such as zirconium oxide (ZrO _{2 ), metal nitrides, and metal oxynitrides.} Generally, as the film forming methods of these thin films, physical vapor deposition methods such as vacuum vapor deposition, sputtering, ion plating, etc.; plasma CVD (Chemical Vapor Deposition, chemical vapor deposition) method, and catalyst chemical vapor deposition methods are known. Phase growth method (Cat-CVD method) and other chemical vapor deposition methods (chemical vapor deposition method), etc. The second layer can also be a plurality of layers.

In the present invention, the polyimide precursor composition can reduce the peel strength by containing a phosphorus compound. Therefore, this application also discloses an invention relating to a method of reducing the peel strength of the laminate, the method is characterized in that it is a method of reducing the peel strength between the base material of the laminate and the polyimide film, and The laminate has the substrate and a polyimide film formed on the substrate, and the polyimide precursor composition for forming the polyimide film contains the phosphorus compound.

In step (c), use the polyimide/substrate laminate obtained in step (c) on a polyimide film (contained in the second layer of the polyimide film surface area layer, inorganic film, etc.) At least one layer selected from a conductive layer and a semiconductor layer is formed thereon. These layers can be formed directly on the polyimide film (including the laminated second layer), or can be formed after other layers required by the laminated device, that is, indirectly.

The conductive layer and/or the semiconductor layer are selected according to the components and circuits required by the target electronic device to select the appropriate conductive layer and (inorganic, organic) semiconductor layer. In step (c) of the present invention, when at least one of the conductive layer and the semiconductor layer is formed, it is also preferable to form at least one of the conductive layer and the semiconductor layer on the polyimide film formed with the inorganic film.

The conductor layer and the semiconductor layer include both of those formed on the entire surface of the polyimide film and those formed on a part of the polyimide film. The present invention can move to step (d) immediately after step (c), or after forming at least one layer selected from a conductive layer and a semiconductor layer in step (c), and then form a device structure, then move to step (d) ).

In the case of manufacturing a TFT liquid crystal display device as a flexible device, for example, a TFT formed of metal wiring, amorphous silicon or polysilicon is formed on a polyimide film with an inorganic film formed on the entire surface as necessary. , Transparent pixel electrode. The TFT includes, for example, a gate metal layer, a semiconductor layer such as an amorphous silicon film, a gate insulating layer, and wiring connected to a pixel electrode. The structure required for the liquid crystal display can also be formed on it by a well-known method. In addition, transparent electrodes and color filters can also be formed on the polyimide film. In the case of manufacturing an organic EL display, for example, a transparent electrode, a light-emitting layer, a hole transport layer, an electron transport layer, etc. can be formed on a polyimide film with an inorganic film formed on the entire surface as necessary. In addition, TFTs can also be formed as needed.

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

Second, in step (d), the substrate and the polyimide film are physically peeled off by external force. "By external force" means applying force to separate the substrate from the polyimide membrane. For example, use human hands or appropriate tools, fixtures, devices, etc. to peel off. When peeling, one or both of the substrate and the polyimide film will bend, but the range of bending the polyimide film is not to affect the conductor layer, semiconductor layer, and semiconductor layer formed on the polyimide film. The scope of damage caused by other structures. For this reason, suitable tools, jigs, devices, etc. can be used for peeling so that the radius of curvature of the polyimide film will not become smaller. Specifically, for example, the following methods can be cited: (i) by inserting a tool such as a blade between the substrate and the polyimide film and moving it to perform peeling; (ii) pulling from the substrate The film is peeled off (in this case, a tool such as a blade can also be used), (iii) the substrate is bent and peeled while ensuring the flatness of the film as much as possible. The peeling is preferably carried out in gas or vacuum, and is usually carried out in air or atmosphere.

On the (semi) product with the polyimide film as the substrate after the substrate is peeled off, the structure or parts required by the device are formed or assembled to complete the device.

In a preferred embodiment of the present invention, the peeling of the substrate and the polyimide film is not carried out by laser irradiation, but is implemented only by a peeling method using external force.

In another embodiment of the present invention, the method of the present invention, that is, the method of using a polyimide precursor containing a phosphorus compound, can be applied as an auxiliary means when peeling cannot be completed by only laser irradiation.

Therefore, another aspect of the present invention relates to a manufacturing method of a flexible electronic device. The method has the following steps: (a) Coating a polyimine precursor composition on a substrate, the polyimine precursor composition contains a polyimine precursor, has a P(=O)OH structure or P(=O)OR (Wherein R is an alkyl group with 4 or more carbons) structure phosphorus compound and solvent; (b) heat-treating the polyimide precursor on the substrate to produce a laminate with a polyimide film laminated on the substrate; (c) forming at least one layer selected from a conductive layer and a semiconductor layer on the polyimide film of the above laminate; (d) Irradiating laser light on the above-mentioned laminated body; and (e) The base material and the polyimide film are peeled off by external force.

Another aspect of the present invention relates to a method for enabling laser peeling when laser radiation peeling cannot be performed. For reasons such as composition limitation and/or insufficient laser output, laser peeling can be achieved by using a polyimide precursor composition containing a phosphorous compound when peeling cannot be performed even if the laser is irradiated. That is, this aspect relates to a manufacturing method of a flexible electronic device, The manufacturing method of the flexible electronic device is characterized by the following steps: (a2) Coating a polyimide precursor composition containing a polyimide precursor and a solvent on the substrate; (b2) Heat treatment of the polyimide precursor on the substrate to produce a laminate with a polyimide film laminated on the substrate; (c2) forming at least one layer selected from a conductive layer and a semiconductor layer on the polyimide film of the above-mentioned laminate; and (e2) Irradiating laser light on the above-mentioned laminated body; and The aforementioned polyimide precursor composition contains a phosphorus compound having a P(=0)OH structure or a P(=0)OR (wherein R is an alkyl group with 4 or more carbons) structure. [Example]

Hereinafter, the present invention will be further described with examples and comparative examples. In addition, the present invention is not limited to the following examples.

＜Evaluation of polyimide film＞ [b*(YI)] Using a UV-visible spectrophotometer/V-650DS (manufactured by JASCO), in accordance with ASTM E313 specifications, measure the b* (=YI; yellowness) of a polyimide film with a thickness of 10 μm and a square size of 3 cm. The light source is D65 and the viewing angle is 2°.

[400 nm light transmittance, total light transmittance] Using a UV-visible spectrophotometer/V-650DS (manufactured by JASCO), measure the light transmittance and total light transmittance of a polyimide film with a thickness of 10 μm and a square size of 5 cm at a wavelength of 400 nm (wavelength 380 nm) ~ 780 nm average transmittance).

[Peel strength] Using TENSILON RTA-500 manufactured by Orientec, the peel strength in the 90° direction was measured at a tensile speed of 2 mm/min.

[Glass transition temperature (Tg)] Cut the polyimide film with a thickness of about 10 μm into short strips with a width of 4 mm and set them as test pieces. Use TMA/SS6100 (manufactured by Seiko Nano Technology Co., Ltd.) with a length of 15 mm , The load is 2 g, and the heating rate is 20°C/min to 500°C. According to the inflection point of the obtained TMA curve, the glass transition temperature (Tg) is calculated.

[1% weight reduction temperature (Td1%)] A polyimide film with a film thickness of about 10 μm was used as a test piece, and a calorimeter measuring device (Q5000IR) manufactured by TA Instruments was used to raise the temperature from 25°C to 600°C at a heating rate of 10°C/min in a nitrogen gas stream. Calculate the 1% weight loss temperature based on the obtained weight curve.

The abbreviations of the compounds used in the following examples are as follows. TFMB: 4,4'-bis(trifluoromethyl)benzidine ODA: 4,4'-diaminodiphenyl ether 4,4'-DDS: 4,4'-diaminodiphenyl sulfide m-TD: 2,2'-dimethyl-4,4'-diaminobiphenyl BAFL: 9,9-bis(4-aminophenyl)sulfonate BAPB: 4,4'-bis(4-aminophenoxy)biphenyl 6FDA: 4,4'-(2,2-hexafluoroisopropylidene) diphthalic dianhydride PMDA-HS: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride BPADA: 5,5'-((propane 2-2-diylbis(1,4-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) CpODA: Norman-2-spiro-α-cyclopentanone-α'-spiro-2''-normanthane-5,5'',6,6''-tetracarboxylic dianhydride CBDA: Cyclobutane tetracarboxylic dianhydride PPHT: N,N'-(1,4-phenylene)bis(1,3-dioxooctahydroisobenzofuran-5-carboxyamide)

[Table 1]

[Table 2]

[Synthesis Example 1] Add 8.38 g (26.2 millimoles) of TFMB to the nitrogen-substituted reaction vessel, and add 80.03 g of N-methyl-2-pyrrolidone to make the total mass of the added monomer (the sum of the diamine component and the carboxylic acid component) It becomes 20 mass %, and it stirred at room temperature for 30 minutes. 11.62 g (26.2 millimoles) of 6FDA was slowly added to the solution. Stir at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.

[Synthesis Example 2] Add 8.02 g (40.0 millimoles) of ODA to the nitrogen-substituted reaction vessel, and add 83.04 g of N,N-dimethylacetamide to make the total mass of the added monomer (the sum of the diamine component and the carboxylic acid component) It becomes 17 mass %, and it stirred at room temperature for 30 minutes. 8.98 g (40.0 millimoles) of PMDA-HS was slowly added to the solution. Stir at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.

[Synthesis Example 3] Add 6.68 g (20.8 millimoles) of TFMB to the nitrogen-substituted reaction vessel, and add 59.99 g of N-methyl-2-pyrrolidone to make the total mass of the added monomer (the sum of the diamine component and the carboxylic acid component) It becomes 20 mass %, and it stirred at room temperature for 30 minutes. To this solution was slowly added 6.48 g (14.6 millimoles) of 6FDA and 1.85 g (6.3 millimoles) of s-BPDA. Stir at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.

[Synthesis Example 4] Add 10.20 g (31.9 millimoles) of TFMB, 0.16 g (0.6 millimoles) of 4,4'-DDS, and 80.02 g of N,N-dimethylacetamide into the reaction vessel replaced by nitrogen. The total monomer mass (the sum of the diamine component and the carboxylic acid component) became 20% by mass, and the mixture was stirred at room temperature for 30 minutes. 0.17 g (0.3 millimoles) of BPADA and 9.47 g (32.2 millimoles) of s-BPDA were slowly added to the solution. Stir at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.

[Synthesis Example 5] Add 10.93 g (51.5 millimoles) of m-TD to the nitrogen-replaced reaction vessel, and add 78.01 g of N-methyl-2-pyrrolidone to make the total mass of the added monomer (the diamine component and the carboxylic acid component) The sum) becomes 22% by mass, and the mixture is stirred at room temperature for 30 minutes. CpODA 1.98 g (5.1 millimoles) and CBDA 9.88 g (46.3 millimoles) were slowly added to the solution. Stir at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.

[Synthesis Example 6] Add BAFL 13.55 g (38.9 millimoles), BAPB 33.44 g (90.8 millimoles), and add 395.02 g of N-methyl-2-pyrrolidone to the reaction vessel replaced with nitrogen to make the total mass of added monomers ( The sum of the diamine component and the carboxylic acid component) became 21% by mass, and the mixture was stirred at room temperature for 30 minutes. To this solution, 12.46 g (32.4 millimoles) of CpODA and 45.55 g (97.2 millimoles) of PPHT were slowly added. Stir at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.

[Example 1] 1.6 mg (0.017 mmol) of methylphosphonic acid and 0.56 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 30.17 g of the polyamide solution obtained in Synthesis Example 1 (the total monomer content in the polyamide acid solution is 15.8 millimoles) was added to the solution, and stirred at room temperature for 12 hours to obtain a uniform and viscous polymer. Precursor solution of imine. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.11 mol%.

The polyamide acid solution was coated on the glass plate of the substrate by a spin coater, and the coating film was heated from 30°C to 350°C at a heating rate of 3°C/min in a nitrogen atmosphere at 350°C. Heat treatment for 10 minutes to form a polyimide film with a thickness of 10 μm on the glass plate. Regarding the peel strength, a test sample with a width of 1 inch (25.4 mm) was prepared from the obtained polyimide film/glass laminate and measured. Regarding the tensile test, the obtained polyimide film/glass laminate was immersed in water, then the polyimide film was peeled from the glass plate, and after drying, it was cut into a predetermined size to prepare a test sample and the characteristics were measured. In the following examples, a tensile test sample was also made in the same manner for measurement. Regarding the optical properties, the polyimide film was mechanically peeled from the polyimide film/glass laminate, cut into a predetermined size, and a test sample was prepared and measured. The same is true in the following examples, but for the comparative example in which the peel strength is high and mechanical peeling cannot be achieved, a measurement sample is produced in the same manner as the sample for tensile test. The results are shown in the table.

[Example 2] 2.2 mg (0.023 millimoles) of methylphosphonic acid and 0.53 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. Add 30.00 g of the polyamide solution obtained in Synthesis Example 2 (the total monomer content in the polyamide acid solution is 24.0 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.10 mol%. The polyamide acid solution was coated on the glass plate of the substrate by a spin coater, and the coating film was heated from 30°C to 350°C at a heating rate of 3°C/min in a nitrogen atmosphere at 350°C. Heat treatment for 10 minutes to form a polyimide film with a thickness of 10 μm on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.

[Example 3] 1.6 mg (0.017 mmol) of methylphosphonic acid and 0.53 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. Add 30.02 g of the polyamide acid solution obtained in Synthesis Example 3 (the total monomer content in the polyamide acid solution is 16.7 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.10 mol%.

The polyamide acid solution was coated on the glass plate of the substrate by a spin coater, and the coating film was heated from 30°C to 350°C at a heating rate of 3°C/min in a nitrogen atmosphere at 350°C. Heat treatment for 10 minutes to form a polyimide film with a thickness of 10 μm on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.

[Example 4] Add 1.9 mg (0.020 millimoles) of p-methylphosphonic acid to 29.99 g of the polyamide acid solution obtained in Synthesis Example 4 (the total monomer content in the polyamide acid solution is 20.8 millimoles), and stir at room temperature After 12 hours, a uniform and viscous polyimide precursor solution was obtained. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.10 mol%.

The polyamide acid solution was coated on the glass plate of the substrate by a spin coater, and the coating film was heated from 30°C to 70°C at a heating rate of 2.5°C/min in a nitrogen atmosphere at 70°C Hold for 20 minutes, then increase the temperature from 70°C to 120°C at a heating rate of 2.5°C/min, hold at 120°C for 20 minutes, then increase the temperature from 120°C to 300°C at a heating rate of 4.6°C/min, and perform 5 at 300°C Minute heat treatment to form a polyimide film with a thickness of 10 μm on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.

[Example 5] Add 3.1 mg (0.032 millimoles) of p-methylphosphonic acid to 30.03 g of the polyamide acid solution obtained in Synthesis Example 5 (the total monomer content in the polyamide acid solution is 30.9 millimoles), and stir at room temperature After 12 hours, a uniform and viscous polyimide precursor solution was obtained. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.10 mol%.

The polyamide acid solution was coated on the glass plate of the substrate by a spin coater, and the coating film was heated from 30°C to 80°C at a temperature rise rate of 3°C/min in a nitrogen atmosphere, at 80°C Hold for 30 minutes, and then raise the temperature from 80°C to 260°C at a heating rate of 3°C/min, heat treatment at 260°C for 10 minutes, and form a polyimide film with a thickness of 10 μm on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.

[Example 6] Add 1.9 mg (0.020 millimoles) of methylphosphonic acid and 0.60 g of N-methyl-2-pyrrolidone into the reaction vessel to obtain a homogeneous solution. Add 40.02 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 20.8 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polymer. Precursor solution of imine. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.10 mol%.

The polyamide acid solution was coated on the glass plate of the substrate by a spin coater, and the coating film was heated from 30°C to 310°C at a temperature rise rate of 5°C/min under a nitrogen atmosphere, at 310°C Heat treatment for 20 minutes to form a polyimide film with a thickness of 10 μm on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.

[Comparative Example 1] Except that the polyimide solution obtained in Synthesis Example 6 was used as it was, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured. However, regarding the peeling test, although I tried to prepare a test sample, the adhesion force between the glass plate and the polyimide film was too large, and the lift-up portion of the film could not be produced and the measurement could not be performed.

[Comparative Example 2] 10 mg (0.10 mmol) of methylphosphonic acid and 10.02 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 14.5 mg of this solution was added to 30.00 g of the polyamide solution obtained in Synthesis Example 6 (the total monomer content in the polyamide solution was 15.6 millimoles), and stirred at room temperature for 12 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.001 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 7] 10 mg (0.10 mmol) of methylphosphonic acid and 10.01 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 149.9 mg of this solution was added to 29.98 g of the polyamide solution obtained in Synthesis Example 6 (the total monomer content in the polyamide solution was 15.5 millimoles), and stirred at room temperature for 12 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.01 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 8] 49.9 mg (0.52 millimoles) of methylphosphonic acid and 5.07 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 50.2 mg of this solution was added to 20.01 g of the polyamide solution obtained in Synthesis Example 6 (the total monomer content in the polyamide solution was 10.4 millimoles), and stirred at room temperature for 12 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.05 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 9] 7.7 mg (0.080 millimoles) of methylphosphonic acid and 0.52 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 30.14 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 15.6 millimoles) was added to the solution, and stirred at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 0.5 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 10] 12.0 mg (0.13 mmol) of methylphosphonic acid and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a homogeneous solution. 20.16 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 10.5 millimoles) was added to the solution, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 1.2 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Comparative Example 3] 49.8 mg (0.52 millimoles) of methylphosphonic acid and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 20.03 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 10.4 millimoles) was added to the solution, and stirred at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of methylphosphonic acid to the total amount of polyimine monomer is 5.0 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured. However, the peel strength between the glass plate and the polyimide film was too low, and it peeled off naturally during the process of making the peel test sample.

[Example 11] Add 2.4 mg (0.021 millimoles) of phosphoric acid and 0.60 g of N-methyl-2-pyrrolidone into the reaction vessel to obtain a homogeneous solution. Add 43.29 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 22.4 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of phosphoric acid to the total amount of polyimide monomer is 0.09 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 12] 9.2 mg (0.080 millimoles) of phosphoric acid and 0.51 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a homogeneous solution. Add 30.00 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 15.6 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of phosphoric acid to the total amount of polyimide monomer is 0.51 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 13] 12.2 mg (0.106 millimoles) of phosphoric acid and 0.53 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a homogeneous solution. Add 19.99 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 10.4 millimoles) to the solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of phosphoric acid to the total amount of polyimide monomer is 1.0 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 14] 4.5 mg (0.017 mmol) of tributyl phosphate and 0.60 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. Add 35.96 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 18.6 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polymer. Precursor solution of imine. Calculated based on the added amount, the ratio of tributyl phosphate to the total amount of polyimide monomer is 0.09 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 15] 32.7 mg (0.123 mmol) of tributyl phosphate and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a homogeneous solution. 20.06 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 10.4 millimoles) was added to the solution, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of tributyl phosphate to the total amount of polyimide monomer is 1.2 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Example 16] 4.4 mg (0.0201 millimoles) of diphenylphosphinic acid and 0.61 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a homogeneous solution. Add 40.11 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 20.8 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polymer. Precursor solution of imine. Calculated based on the added amount, the ratio of diphenylphosphinic acid to the total amount of polyimide monomers was 0.10 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Comparative Example 4] 3.5 mg (0.023 mmol) of diethyl methylphosphonate and 0.61 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. Add 40.06 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 20.8 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polymer. Precursor solution of imine. Calculated based on the added amount, the ratio of diethyl methylphosphonate to the total amount of polyimine monomer is 0.11 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Comparative Example 5] 4.6 mg (0.021 mmol) of tributylphosphine oxide and 0.79 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. Add 39.97 g of the polyamide acid solution obtained in Synthesis Example 6 (the total monomer content in the polyamide acid solution is 20.7 millimoles) to this solution, and stir at room temperature for 12 hours to obtain a uniform and viscous polyamide solution. Precursor solution of imine. Calculated based on the added amount, the ratio of tributyl phosphine oxide to the total amount of polyimide monomer is 0.10 mol%. Except for using this polyimide solution, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

[Comparative Examples 6-9] Except that the polyimide solutions obtained in Synthesis Examples 1 to 3 and 5 were used as they were, a polyimide film was formed in the same manner as in Example 6, and various characteristics were measured.

Regarding the composition of the Examples and Comparative Examples and the obtained films, the measurement results of b*, peeling characteristics, and 400 nm transmittance are shown in Tables 3 to 7. The physical properties of the films were further measured for the Examples, and the results are shown in Table 8. ~10 in.

[table 3] composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 TFMB/6FDA ○ ODA/PMDA-HS ○ TFMB/s-BPDA/6FDA ○ TFMB/DDS/s-BPDA/BPADA ○ m-TD/CpODA/CBDA ○ BAFL/BAPB/CpODA/PPHT ○ Add compound Methylphosphonic acid mol% 0.1 0.1 0.1 0.1 0.1 0.1 b* 0.8 1.5 0.9 1.8 0.4 0.8 Peel strength/N/in. 0.01 0.03 0.01 0.02 0.02 0.06 400 nm transmittance% 85.9 84.3 81.9 60.5 88.7 85.8 The unit N/in is N/25.4 mm.

[Table 4] composition Example 7 Example 8 Example 6 Example 9 Example 10 Comparative example 1 Comparative example 2 Comparative example 3 BAFL/BAPB/CpODA/PPHT ○ ○ ○ ○ ○ ○ ○ ○ Add compound Methylphosphonic acid (mol%) 0.01 0.05 0.1 0.5 1 0 0.001 5 Phosphoric acid (mol%) Tributyl phosphate (mol%) b* 0.9 0.8 0.7 0.9 0.8 0.7 0.9 1.2 Peel strength/N/in. 0.8 0.09 0.06 0.02 0.03 large* 1.8 small* 400 nm transmittance% 86.4 87.0 85.8 86.7 87.1 85.9 86.6 84.4 *)large: The peel strength is too large to make a test sample. small: The peel strength is too small, and it peels off naturally during the process of making the test sample.

[table 5] composition Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 BAFL/BAPB/CpODA/PPHT ○ ○ ○ ○ ○ ○ Add compound Methylphosphonic acid (mol%) Phosphoric acid (mol%) 0.1 0.5 1 Tributyl phosphate (mol%) 0.1 1 Diphenylphosphinic acid (mol%) 0.1 b* 0.9 0.9 1.0 0.9 1.1 0.9 Peel strength/N/in. 0.01 0.04 0.36 0.06 0.4 0.8 400 nm transmittance% 85.6 86.4 85.7 85.7 85.1 85.8

[Table 6] composition Comparative example 4 Comparative example 5 BAFL/BAPB/CpODA/PPHT ○ ○ Add compound Diethyl methylphosphonate (mol%) 0.1 Tributyl phosphine oxide (mol%) 0.1 b* 0.9 0.9 Peel strength/N/in. 1.1 2.4 400 nm transmittance% 85.4 85.7

[Table 7] composition Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 TFMB/6FDA ○ ODA/PMDA-HS ○ TFMB/s-BPDA/6FDA ○ m-TD/CpODA/CBDA ○ Add compound No addition b* 0.8 1.5 0.9 0.4 Peel strength/N/in. 3.3 1.7 2.6 1.2 400 nm transmittance% 86.1 84.4 82.6 88.5

[Table 8] Physical properties Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Tg(TMA)/℃ 324 333 323 304 325 300 Td 1%/℃ - - - - - 413 400 nm transmittance% 85.9 84.3 81.9 60.5 88.7 85.8 Total light transmittance/%T (380～780 nm) 90.6 89.6 89.6 85.5 90.1 88.5 In the table-means not determined.

[Table 9] Physical properties Example 7 Example 8 Example 9 Example 10 Tg(TMA)/℃ 301 299 302 311 Td 1%/℃ - - - - 400 nm transmittance% 86.4 87.0 86.7 87.1 Total light transmittance/%T (380～780 nm) 89.6 89.7 89.3 89.7

[Table 10] Physical properties Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Tg(TMA)/℃ 302 - - 301 - 300 Td 1%/℃ 415 - - 419 407 415 400 nm transmittance% 85.6 86.4 85.7 85.7 85.1 85.8 Total light transmittance/%T (380～780 nm) 88.5 89.4 89.4 88.5 - 88.5 [Industrial availability]

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

Claims (17)

A polyimide precursor composition, which is characterized in that it contains: Polyimide precursor; Phosphorus compound, which has a P(=O)OH structure or P(=O)OR (wherein R is an alkyl group with 4 or more carbons) structure, and is relative to the total monomer units of the polyimide precursor , Which is more than 0.001 mol% and less than 5 mol%; and Solvent (However, the following condition (A) is satisfied) (A) The above-mentioned polyimine precursor is not only a polyimine precursor obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine. The composition of claim 1, wherein the content of the phosphorus compound is 0.01 mol% or more relative to the total monomer units of the polyimide precursor. The composition of claim 1 or 2, wherein the above-mentioned phosphorus compound does not include a compound having an aryl group directly bonded to P. The composition according to any one of claims 1 to 3, wherein the molecular weight of the above-mentioned phosphorus compound is less than 400. The composition according to any one of claims 1 to 4, wherein the polyimide precursor includes a repeating unit, and the repeating unit is selected from the structure represented by the following general formula (I) and the general formula (I) A structure in which at least one of the amide structure is imidized, [化1]

(In the general formula (I), X ₁ is a tetravalent aliphatic or aromatic group, Y ₁ is a divalent aliphatic or aromatic group, and R ₁ and R ₂ are independently hydrogen atoms and carbon numbers 1-6 alkyl group or C3-9 alkylsilyl group). The composition of claim 5, wherein, relative to the total repeating units, X ₁ is a tetravalent group _{having an alicyclic structure and Y 1 is one} of the repeating units represented by the general formula (I) having a divalent group of an alicyclic structure The content is less than 50 mol%. The composition of claim 5, wherein X ₁ in the general formula (I) is a tetravalent group _{having an aromatic ring, and Y 1} is a divalent group having an aromatic ring. The composition of claim 5, wherein X ₁ in the general formula (I) is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. The composition of claim 5, wherein X ₁ in the general formula (I) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure. For example, the composition of claim 5, which contains the repeating unit X ₁ of the general formula (I) having a tetravalent group having an alicyclic structure at a ratio of more than 60% in the total repeating unit (however, relative to the total repeating unit, X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is a divalent group having an alicyclic structure. The content of the repeating unit represented by the general formula (I) is 50 mol% or less). A manufacturing method of a flexible electronic device, which has the following steps: (a) Coating a polyimine precursor composition on a substrate, the polyimine precursor composition contains a polyimine precursor, has a P(=O)OH structure or P(=O)OR (Wherein R is an alkyl group with 4 or more carbons) structure phosphorus compound and solvent; (b) Heat treatment of the polyimide precursor on the substrate to produce a laminate with a polyimide film laminated on the substrate; (c) forming at least one layer selected from a conductive layer and a semiconductor layer on the polyimide film of the above-mentioned laminate; and (d) The base material and the polyimide film are peeled off by external force. The manufacturing method of claim 11, wherein the polyimine precursor composition is the polyimine precursor composition of any one of claims 1 to 10. The manufacturing method of claim 11 or 12, wherein the substrate is a glass plate. The manufacturing method according to any one of claims 11 to 13, wherein laser irradiation is not performed in the step of peeling off the base material and the polyimide film. A method for reducing the peel strength of a laminate, characterized in that it is a method of reducing the peel strength between a base material of the laminate and a polyimide film, the laminate having the base material and being formed on the base material Of polyimide film, and The polyimide precursor composition used to form the above polyimide film contains a P(=O)OH structure or P(=O)OR (where R is an alkyl group with 4 or more carbons) structure Phosphorus compounds. The method according to claim 15, wherein the polyimine precursor composition is the polyimine precursor composition according to any one of claims 1 to 10. The method of claim 15 or 16, wherein the substrate is a glass plate.