TW202105415A - Laminate - Google Patents

Abstract

A laminate in which a polyimide film is adhered to a glass substrate or a silicon substrate and a metal film or an oxide semiconductor film is then laminated to the polyimide film, wherein the thickness of the metal film or oxide semiconductor film is within a range from 1 to 400 nm, and the water content of the polyimide film is within a range from 1,000 to 35,000 ppm by mass.

Description

Laminated body

The present invention relates to a laminated body, in detail, it relates to a polyimide film in which a polyimide film is adhered to a glass substrate or a silicon substrate, and a metal film or an oxide semiconductor film is further laminated on the polyimide film Laminated body.

As far as polyimide resin is concerned, various applications in the fields of electrical and electronic parts have been explored. For example, for the purpose of lightweight and flexible devices, it is hoped to replace the glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates. Research on polyimide films suitable for the plastic substrates is underway. get on. In an image display device, when the light emitted by the display element is emitted through a plastic substrate, the plastic substrate is required to have colorless transparency. In addition, when the light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, a touch panel, etc.) In addition to requiring colorless transparency, it also requires high optical isotropy (that is, low Rth).

In addition, when a polyimide film is used as a substrate, it will be formed on the polyimide film due to various steps such as sputtering and etching steps for producing oxide semiconductor films such as indium tin oxide (ITO) films. Make electronic circuits for the purpose. When manufacturing the intended electronic circuit on the polyimide film, in order to ensure the flatness of the polyimide film, the polyimide film is made to adhere closely to a hard support such as a glass plate. At this time, if the polyimide film is not closely adhered to the support, defects may occur in the manufacturing process. In addition, after these processes, a step of peeling the polyimide film from the support is required. This peeling step is performed after cooling the molded body on the substrate to room temperature to about 50°C.

As a method of adhering the polyimide film to the support, in addition to the method of adding an adhesive to the polyimide itself, it is also known that a so-called peeling layer is interposed between the polyimide film and the support. In order to ensure the tightness in the manufacturing process, etc.

In addition, as a method of peeling the polyimide film from the support, for example, the following method is known. (1) Obtain a structure containing polyimide resin/support, and then by irradiating a laser from the support side, and by performing an ablation process on the interface of the polyimide resin, the polyimide resin is added The method of peeling (for example, refer to Patent Document 1). The types of lasers include solid (YAG) lasers and gas (UV excimer) lasers, which use a spectrum of 308nm. (2) Before coating the resin composition on the support, a release layer is formed on the support, and then a structure containing the polyimide resin film/release layer/support is obtained, and then the polyimide resin film is mechanically Method of peeling off sexually (for example, refer to Patent Document 2). As for the release layer, there are methods using Parylene (registered trademark, manufactured by Parylene Japan) and tungsten oxide, and methods using vegetable oil-based, silicone-based, fluorine-based, and alkyd-based mold release agents. In addition, sometimes the laser irradiation described in (1) above may be used.

In addition, Patent Document 3 discloses a method in which a resin substrate is fixed to a support substrate by an adhesive layer, electronic components are formed on the resin substrate, and then the electronic device including the electronic components and the resin substrate is peeled from the support substrate. It uses an adhesive layer whose main component is a material that reduces the adhesive force with the support substrate by contact with moisture.

On the other hand, Patent Document 4 discloses that considering the viewpoint of the imidization of polyimide acid and the viewpoint of the storage stability of the resin composition, the reduction in the resin composition containing the polyimide precursor and the organic solvent Moisture content. That is, it is thought that due to the influence of moisture, some acid anhydride groups of the acid dianhydride monomer will be hydrolyzed into carboxyl groups, and will not be high molecular weight but remain in a low molecular state. In addition, it is believed that water will participate in the decomposition and recombination of the polyimide precursor, thereby affecting the viscosity stability of the resin composition during storage. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Special Publication No. 2007-512568 [Patent Document 2] JP 2010-067957 A [Patent Document 3] JP 2016-021384 A [Patent Document 4] JP 2018-145440 A

[The problem to be solved by the invention]

In the above method (1), the resin substrate formed on the substrate may be damaged during laser irradiation, which may become a problem. In addition, an expensive laser irradiation device must be introduced, which poses a cost issue. In the above method (2), although a laser irradiation device is not required, depending on the type of polyimide, sometimes the peeling layer may not fully perform its function. In the method of Patent Document 3, when forming an electronic component, in order to prevent the adhesive layer from contacting with moisture and thereby not reducing the adhesive force, it is necessary to form a sealing layer that seals the exposed portion of the adhesive layer. On the other hand, when the electronic device is peeled off after the electronic component is formed, in order to expose the adhesive layer to moisture, the sealing layer must be removed before peeling. Therefore, the method of Patent Document 3 is a complicated process as a whole. In addition, in order to be exposed to moisture, it must be installed in a high-humidity environment with a humidity of 90% or more. It is difficult to control the moisture content, and there is a problem that it is difficult to ensure stable peelability.

The present invention is made in view of such a situation, and aims to provide a laminate in which a polyimide film is closely adhered to a glass substrate or a silicon substrate, and a metal film or oxidized film is further laminated on the polyimide film. The polyimide film has excellent colorless transparency and optical isotropy, and can easily and stably peel the polyimide film from the glass substrate or silicon substrate. [Means to solve the problem]

The inventors of the present application have unexpectedly discovered that the above-mentioned problems can be solved by deliberately containing an optimal amount of water, which has been sought to be reduced in the past, in the film. The present invention has been completed based on such findings.

That is, the present invention relates to the following. <1> A laminated body formed by closely adhering a polyimide film on a glass substrate or a silicon substrate, and further laminating a metal film or an oxide semiconductor film on the aforementioned polyimide film; The thickness of the metal film or the oxide semiconductor film is 1 to 400 nm, and the moisture content of the polyimide film is 1,000 to 35,000 mass ppm. <2> The laminate according to the above <1>, wherein the peel strength of the polyimide film when peeled from a glass substrate or a silicon substrate is 20 gf/cm or less. <3> The laminate according to the above <1> or <2>, wherein the film thickness of the polyimide film is 3 to 20 μm. <4> The laminate according to any one of the above <1> to <3>, wherein the oxide semiconductor film is selected from the group consisting of indium tin oxide, amorphous silicon, indium-gallium-zinc oxide, and low-temperature polysilicon At least one of the groups. <5> A conductive film obtained by peeling and removing the aforementioned glass substrate or silicon substrate from the laminate of any one of the above-mentioned <1> to <4>. <6> A method of manufacturing a conductive film, including the following steps: Laminating polyimide film on glass substrate or silicon substrate; Adjust the moisture content of the aforementioned polyimide film to 1,000-35,000 ppm by mass; Laminating a metal film or oxide semiconductor film with a thickness of 1 to 400 nm on the polyimide film; and Peel off the glass substrate or silicon substrate. <7> The method for producing a conductive film according to the above <6>, wherein the step of adjusting the moisture content of the polyimide film is to keep the polyimide film at 10-40°C and 40-80% More than 20 hours under RH temperature and humidity environment. <8> The method for manufacturing a conductive film as described in the above <6> or <7>, wherein the step of laminating a metal film or an oxide semiconductor film on the polyimide film is performed by physical vapor deposition or chemical vaporization. Plating method. [Effects of Invention]

The laminate of the present invention can be easily and stably peeled even when the polyimide film is mechanically peeled from a glass substrate or a silicon substrate. Therefore, the laminate of the present invention can contribute to the simplification of the manufacturing process of the flexible electronic device with the resin substrate or the improvement of its productivity. In addition, the polyimide film is excellent in colorless transparency and optical isotropy. Therefore, a thin film peeled from a glass substrate or a silicon substrate is suitable as a resin substrate for flexible electronic devices.

Hereinafter, an embodiment of the present invention will be described. The content of the present invention is not limited to the embodiments described below. In addition, in this manual, the terms "A to B" in the description of numerical values mean "A or more and B or less" (A<B) or "A or less and B or more" (A>B). In addition, in the present invention, a combination of preferred aspects is a better aspect.

In the laminated system of the present invention, a polyimide film is closely adhered to a glass substrate or a silicon substrate, and a metal film or an oxide semiconductor film is further laminated on the polyimide film. The metal film Or the thickness of the oxide semiconductor film is 1 to 400 nm, and the moisture content of the aforementioned polyimide film is 1,000 to 35,000 mass ppm.

(Glass substrate or silicon substrate) The glass substrate or the silicon substrate is not particularly limited, as long as it has the strength to support the polyimide film when manufacturing an electronic device (conductive film) using the polyimide film as a substrate. The type of glass is also not particularly limited, and alkali-free glass (borosilicate glass), alkali glass, soda glass, non-fluorescent glass, phosphoric acid-based glass, boric-acid-based glass, quartz, etc. can be used. In order to make the adhesion with the polyimide film better, the flatness of the upper surface of the glass substrate or the silicon substrate should be higher. Specifically, the surface roughness Rmax is preferably 10 μm or less, and Rmax is more preferably 1 μm or less.

(Polyimide film) The laminated system of the present invention makes the polyimide film adhere closely to the glass substrate or the silicon substrate. The polyimide film should preferably be directly adhered to the glass substrate or silicon substrate, and it is preferable that no adhesive layer is interposed between the glass substrate or the silicon substrate and the polyimide film.

The moisture content of the polyimide film in the present invention is 1,000 to 35,000 mass ppm, preferably 3,000 to 30,000 mass ppm, and more preferably 5,000 to 25,000 mass ppm. If the moisture content of the polyimide film is within this range, the polyimide film can be stably peeled from the glass substrate or the silicon substrate after the electronic device is manufactured.

The film thickness of the polyimide film is preferably 3-20 μm, more preferably 4-15 μm, and still more preferably 5-10 μm. If the film thickness of the polyimide film is within this range, the polyimide film will not be damaged in the manufacture of electronic devices, and the manufacture of electronic devices becomes easy. After the manufacture of electronic devices, it can be stably peeled off from the glass substrate or silicon substrate. . In addition, the film thickness of the polyimide film can be determined by physical measurement using a micrometer or the like, or optical observation using a laser microscope, etc., by measuring the height of the contact surface between the upper surface of the film and the glass.

The peel strength of the polyimide film when peeled from a glass substrate or a silicon substrate is preferably 20 gf/cm or less, more preferably 15 gf/cm or less, and still more preferably 10 gf/cm or less. If the peel strength is within this range, the polyimide film will adhere to the glass substrate or silicon substrate without peeling during the manufacture of electronic devices, and the electronic device can be stably peeled from the glass substrate or silicon substrate after manufacture.

The polyimide film of the present invention is excellent in colorless transparency and optical isotropy. The ideal physical properties of the polyimide film of the present invention are as follows.

When a film with a thickness of 10 μm is formed, the total light transmittance is preferably 88% or more, more preferably 88.5% or more, and still more preferably 89% or more. When a film with a thickness of 10 μm is formed, the yellow index (YI) is preferably 4.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. When a film with a thickness of 10 μm is formed, b* is preferably 2.0 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.

When a film with a thickness of 10 μm is formed, the absolute value of the thickness retardation (Rth) is preferably 100 nm or less, more preferably 60 nm or less, and still more preferably 35 nm or less. When it is in this range, the optical isotropy is excellent.

The tensile strength is preferably 60 MPa or more, more preferably 70 MPa or more, and still more preferably 80 MPa or more. The tensile modulus of elasticity is preferably 2.0 GPa or more, more preferably 2.5 GPa or more, and still more preferably 3.0 GPa or more.

The glass transition temperature (Tg) of the polyimide resin constituting the polyimide film in the present invention is preferably 230°C or higher, more preferably 250°C or higher, and still more preferably 270°C or higher.

A preferred example of the polyimide resin that can be used in the present invention is shown, but the present invention is not limited to this.

[Polyimide resin 1] Polyimide resin 1 has a structural unit A1 derived from tetracarboxylic dianhydride and a structural unit B1 derived from diamine, and the structural unit A1 includes a structural unit (A-11) derived from a compound represented by the following formula (a-11), With the structural unit (A-12) derived from the compound represented by the following formula (a-12), the structural unit B1 includes the structural unit (B-11) derived from the compound represented by the following formula (b-11), and the structural unit (B-11) derived from the compound represented by the following formula ( b-12) The structural unit of the compound represented by (B-12).

[化1]

＜Construction unit A1＞ The structural unit A1 is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin 1, and includes a structural unit (A-11) derived from a compound represented by the following formula (a-11), and a structural unit derived from the following formula ( a-12) represents the structural unit (A-12) of the compound.

[化2]

The compound represented by the formula (a-11) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride. The compound represented by the formula (a-12) is 4,4'-oxydiphthalic anhydride. Since the constituent unit A1 includes both the constituent unit (A-11) and the constituent unit (A-12), the colorless transparency, optical isotropy, and chemical resistance of the film can be improved. The structural unit (A-11) particularly contributes to the improvement of colorless transparency and optical isotropy, and the structural unit (A-12) particularly contributes to the improvement of chemical resistance.

The ratio of the constituent unit (A-11) in the constituent unit A1 is preferably 5 to 95 mol%, more preferably 15 to 95 mol%, still more preferably 20 to 90 mol%, particularly preferably 50 to 90 Mol%. The ratio of the constituent unit (A-12) in the constituent unit A1 is preferably 5 to 95 mol%, more preferably 5 to 85 mol%, still more preferably 10 to 80 mol%, particularly preferably 10 to 50 Mol%. The total ratio of the constituent units (A-11) and (A-12) in the constituent unit A1 is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more, especially preferred It is more than 99 mol%. The upper limit of the total ratio of the structural units (A-11) and (A-12) is not particularly limited, and that is, it is 100 mol%. The structural unit A1 may consist of only the structural unit (A-11) and the structural unit (A-12).

The structural unit A1 may contain structural units other than the structural units (A-11) and (A-12). The tetracarboxylic dianhydride that provides such a structural unit is not particularly limited, and examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 9,9'-bis (3,4-Dicarboxyphenyl) dianhydride, and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and other aromatic tetracarboxylic dianhydrides (except, formula (a-12) ) Except for the compounds indicated); 1,2,3,4-cyclobutanetetracarboxylic dianhydride and norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane -5,5'',6,6''-tetracarboxylic dianhydride and other alicyclic tetracarboxylic dianhydrides (except for the compound represented by formula (a-11)); and 1,2,3,4 -Aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride. In addition, in this specification, aromatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing more than one aromatic ring, and alicyclic tetracarboxylic dianhydride refers to containing more than one alicyclic ring and no aromatic Cyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride mean tetracarboxylic dianhydride that does not contain aromatic or alicyclic rings. The structural units arbitrarily contained in the structural unit A1 (that is, structural units other than the structural units (A-11) and (A-12)) may be one type or two or more types.

<Constitutional unit B1> The structural unit B1 is a structural unit derived from a diamine in the polyimide resin, and includes a structural unit (B-11) derived from a compound represented by the following formula (b-11), and a structural unit derived from the following formula (b-11) (b-12) represents the structural unit (B-12) of the compound. [化3]

The compound represented by the formula (b-11) is 3,3'-diaminodiphenyl sulfide. Since the constituent unit B1 includes the constituent unit (B-11), the optical isotropy and chemical resistance of the film can be improved. The compound represented by the formula (b-12) is bis[4-(4-aminophenoxy)phenyl] sulfide. Since the constituent unit B1 includes the constituent unit (B-12), the tensile elongation of the film can be improved.

The ratio of the constituent unit (B-11) in the constituent unit B1 is preferably 5 to 95 mol%, more preferably 15 to 95 mol%, still more preferably 20 to 90 mol%, particularly preferably 50 to 90 Mol%. The ratio of the constituent unit (B-12) in the constituent unit B1 is preferably 5 to 95 mol%, more preferably 5 to 85 mol%, still more preferably 10 to 80 mol%, particularly preferably 10 to 50 Mol%. The total ratio of the constituent units (B-11) and (B-12) in the constituent unit B1 is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more, especially preferred It is more than 99 mol%. The upper limit of the total ratio of the constituent units (B-11) and (B-12) is not particularly limited, and that is, it is 100 mol%. The structural unit B1 may consist of only the structural unit (B-11) and the structural unit (B-12).

The structural unit B1 may contain structural units other than the structural units (B-11) and (B-12). The diamine that provides such a structural unit is not particularly limited, and examples include 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2'-Dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl ether, 4,4' -Diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylaniline , 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, α,α'-bis(4-aminophenyl) )-1,4-Diisopropylbenzene, N,N'-bis(4-aminophenyl)p-xylylenedimethamide, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 9,9- Aromatic diamines such as bis(4-aminophenyl) pyridium and 4,4'-diamino-2,2'-bistrifluoromethyldiphenyl ether (except, formula (b-11) or ( b-12) Except for the compounds indicated); 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane and other alicyclic diamines; and ethylenediamine And aliphatic diamines such as hexamethylene diamine. In addition, in this specification, aromatic diamine means diamine containing one or more aromatic rings, alicyclic diamine means diamine containing one or more alicyclic rings and no aromatic ring, aliphatic diamine It means a diamine that does not contain aromatic or alicyclic rings. The structural units arbitrarily contained in the structural unit B1 (that is, structural units other than the structural units (B-11) and (B-12)) may be one type or two or more types.

As the diamine that provides the structural unit optionally contained in the structural unit B1, a compound represented by the following formula (b-13-1), a compound represented by the following formula (b-13-2), or the following formula (b-13- 3) The compound represented and the compound represented by the following formula (b-13-4). That is, in the polyimide resin of one aspect of the present invention, the structural unit B1 may further contain the structural unit (B-13), and the structural unit (B-13) is selected from the following formula (b-13) -1) the structural unit (B-13-1) of the compound represented by the following formula (b-13-2) the structural unit (B-13-2) from the compound represented by the following formula (b-13-3) At least one of the structural unit (B-13-3) of the compound represented by) and the group consisting of the structural unit (B-13-4) from the compound represented by the following formula (b-13-4).

式(b-13-2)中，R各自獨立地為氫原子、氟原子或甲基。[化4]

In the formula (b-13-2), R is each independently a hydrogen atom, a fluorine atom, or a methyl group.

The compound represented by the formula (b-13-1) is 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA). Since the constituent unit B1 contains the constituent unit (B-13-1), the colorlessness and transparency of the film can be improved.

In formula (b-13-2), R is each independently selected from the group consisting of a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 5 carbon atoms, and is a hydrogen atom, a fluorine atom, or a methyl group, preferably hydrogen atom. The compound represented by the formula (b-13-2) includes 9,9-bis(4-aminophenyl) pyrene, 9,9-bis(3-fluoro-4-aminophenyl) pyrene, and 9, 9-bis(3-methyl-4-aminophenyl) sulfonate, etc., preferably at least one selected from the group consisting of these 3 compounds, which is 9,9-bis(4-aminophenyl)基)茀 is better. Since the constituent unit B1 contains the constituent unit (B-13-2), the optical isotropy and heat resistance of the film can be improved.

The compound represented by the formula (b-13-3) is 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane. Since the constituent unit B1 contains the constituent unit (B-13-3), the colorlessness and transparency of the film can be improved.

The compound represented by the formula (b-13-4) is 2,2'-bis(trifluoromethyl)benzidine. Since the constituent unit B1 contains the constituent unit (B-13-4), the colorlessness, transparency, chemical resistance, and mechanical properties of the film can be improved.

When the structural unit B1 contains the structural unit (B-11), the structural unit (B-12), and the structural unit (B-13), the structural unit (B-11) and the structural unit (B-12) in the structural unit B1 The total ratio is preferably 70-95 mol%, more preferably 75-95 mol%, and still more preferably 75-90 mol%, and the ratio of the constituent unit (B-13) in the constituent unit B1 is preferably 5 ~30 mol%, more preferably 5-25 mol%, still more preferably 10-25 mol%. The total ratio of the structural unit (B-11), the structural unit (B-12), and the structural unit (B-13) in the structural unit B1 is preferably 75 mol% or more, more preferably 80 mol% or more, and More preferably, it is 90 mol% or more, and particularly preferably, it is 99 mol% or more. The upper limit of the total ratio of the structural unit (B-11), the structural unit (B-12), and the structural unit (B-13) is not particularly limited, and is 100 mol%. The structural unit B1 may be composed of only the structural unit (B-11), the structural unit (B-12), and the structural unit (B-13).

The structural unit (B-13) may be only the structural unit (B-13-1), or only the structural unit (B-13-2), or only the structural unit (B-13-3), or It can be only the constituent unit (B-13-4). In addition, the structural unit (B-13) may be a combination of two or more structural units selected from the group consisting of the structural units (B-13-1) to (B-13-4).

The number average molecular weight of the polyimide resin 1, considering the mechanical strength of the obtained polyimide film, is preferably 5,000 to 200,000. In addition, the number average molecular weight of the polyimide resin can be calculated, for example, from a standard polymethyl methacrylate (PMMA) conversion value obtained by gel filtration chromatography measurement.

The polyimide resin 1 may contain structures other than the polyimine chain (a structure in which the structural unit A1 and the structural unit B1 form an amide bond). As a structure other than the polyimine chain which can be contained in a polyimide resin, the structure containing an amide bond etc. is mentioned, for example. The polyimide resin 1 preferably contains a polyimine chain (a structure in which the constituent unit A1 and the constituent unit B1 form an amide bond) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin 1 is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 99% by mass or more.

[Manufacturing method of polyimide resin 1] The polyimide resin 1 can be prepared by combining a tetracarboxylic acid component including a compound providing the above-mentioned structural unit (A-11) and a compound providing the above-mentioned structural unit (A-12) with a compound including the above-mentioned structural unit (B-11). The compound of) and the diamine component that provides the compound of the above-mentioned structural unit (B-12) are produced by reacting.

The compound that provides the structural unit (A-11) may be a compound represented by the formula (a-11), but it is not limited to this, and it may be a derivative thereof within the range that the same structural unit is provided. The derivative can be exemplified by the tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-11) (that is, 1,2,4,5-cyclohexane tetracarboxylic acid) and the alkane of the tetracarboxylic acid Base ester. The compound providing the constituent unit (A-11) is preferably a compound represented by formula (a-11) (that is, dianhydride). Similarly, the compound providing the structural unit (A-12) may be a compound represented by the formula (a-12), but it is not limited to this, and its derivatives may also be provided within the scope of providing the same structural unit. Examples of the derivative include tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by formula (a-12) and alkyl esters of the tetracarboxylic acid. The compound providing the constituent unit (A-12) is preferably a compound represented by formula (a-12) (that is, dianhydride).

The tetracarboxylic acid component preferably contains 5-95% mol% of the compound providing the constituent unit (A-11), more preferably 15-95% mol, still more preferably 20-90 mol%, particularly preferably 50- 90 mol%. The tetracarboxylic acid component preferably contains 5-95 mol% of the compound providing the constituent unit (A-12), more preferably 5-85 mol%, still more preferably 10-80 mol%, particularly preferably 10-80 mol% 50 mol%. The tetracarboxylic acid component preferably contains a total of 50 mol% or more of the compound providing the structural unit (A-11) and the compound providing the structural unit (A-12), more preferably 70 mol% or more, and even more preferably 90 Mole% or more, particularly preferably 99 mole% or more. The upper limit of the total content ratio of the compound providing the structural unit (A-11) and the compound providing the structural unit (A-12) is not particularly limited, that is, it is 100 mol%. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A-11) and the compound providing the structural unit (A-12).

The tetracarboxylic acid component may also include compounds other than the compound providing the constituent unit (A-11) and the compound providing the constituent unit (A-12). Examples of the compound include the above-mentioned aromatic tetracarboxylic dianhydride and alicyclic tetracarboxylic acid. Acid dianhydride, aliphatic tetracarboxylic dianhydride, and their derivatives (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.). The compound arbitrarily contained in the tetracarboxylic acid component (that is, a compound other than the compound providing the structural unit (A-11) and the compound providing the structural unit (A-12)) may be one type or two or more types.

The compound that provides the structural unit (B-11) may be a compound represented by the formula (b-11), but it is not limited to this, and its derivative may be provided within the range of providing the same structural unit. Examples of the derivative include diisocyanates corresponding to the diamine represented by formula (b-11). The compound providing the constituent unit (B-11) is preferably a compound represented by the formula (b-11) (that is, a diamine). The compound that provides the structural unit (B-12) may be a compound represented by the formula (b-12), but it is not limited to this, and its derivative may also be provided within the range of providing the same structural unit. Examples of the derivative include diisocyanates corresponding to the diamine represented by formula (b-12). The compound providing the constituent unit (B-12) is preferably a compound represented by the formula (b-12) (that is, a diamine).

The diamine component preferably contains 5-95% mol% of the constituent unit (B-11), more preferably 15-95% mol, more preferably 20-90 mol%, particularly preferably 50-90 mol% . The diamine component preferably contains 5-95% mol% of the constituent unit (B-12), more preferably 5-85 mol%, still more preferably 10-80 mol%, particularly preferably 10-50 mol% . The total diamine component should preferably contain 50 mol% or more of the constituent units (B-11) and (B-12), more preferably 70 mol% or more, more preferably 90 mol% or more, particularly preferably 99 mol% Ear% or more. The upper limit of the total ratio of the constituent units (B-11) and (B-12) is not particularly limited, and that is, it is 100 mol%. The diamine component may consist only of the structural unit (B-11) and the structural unit (B-12).

The diamine component may also include compounds other than the compound providing the structural unit (B-11) and the compound providing the structural unit (B-12). Examples of the compound include the above-mentioned aromatic diamines, alicyclic diamines, and aliphatic Diamines, and their derivatives (diisocyanates, etc.). The compound arbitrarily contained in the diamine component (that is, a compound other than the compound providing the structural unit (B-11) and the compound providing the structural unit (B-12)) may be one type or two or more types.

The compound arbitrarily contained in the diamine component is preferably a compound that provides the structural unit (B-13) (that is, a compound that provides the structural unit (B-13-1), a compound that provides the structural unit (B-13-2), Provide the compound of the structural unit (B-13-3), and provide the compound of the structural unit (B-13-4)). The compound that provides the constituent unit (B-13) includes the compound represented by the formula (b-13-1), the compound represented by the formula (b-13-2), the compound represented by the formula (b-13-3), and the formula The compound represented by (b-13-4) is not limited thereto, and may be a derivative thereof within the range that can form the same structural unit. Examples of the derivative include diisocyanates corresponding to the diamines represented by formulas (b-13-1) to (b-13-4). The compound providing the constituent unit (B-13) is preferably a compound represented by formula (b-13-1) to formula (b-13-4) (that is, diamine).

When the diamine component includes a compound providing structural unit (B-11), a compound providing structural unit (B-12), and a compound providing structural unit (B-13), the total diamine component should preferably contain 70-95 mol % Of the compound providing structural unit (B-11) and the compound providing structural unit (B-12), more preferably 75-95% mol%, still more preferably 75-90 mol%, preferably containing 5-30 The mole% of the compound providing the constituent unit (B-13) is more preferably 5-25 mole%, and still more preferably 10-25 mole%. The diamine component preferably contains a total of 75 mol% or more of the compound providing the structural unit (B-11), the compound providing the structural unit (B-12), and the compound providing the structural unit (B-13), more preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the total content ratio of the compound providing the structural unit (B-11), the compound providing the structural unit (B-12), and the compound providing the structural unit (B-13) is not particularly limited, that is, 100 Mol%. The diamine component may consist only of the compound which provides the structural unit (B-11), the compound which provides the structural unit (B-12), and the compound which provides the structural unit (B-13).

The compound providing the structural unit (B-13) can only be the compound providing the structural unit (B-13-1), or only the compound providing the structural unit (B-13-2), or it can only provide the structural unit The compound of (B-13-3) may also only provide the compound of the constituent unit (B-13-4). In addition, the compound providing the structural unit (B-13) may also be a combination of two or more compounds selected from the group consisting of the compounds providing the structural unit (B-13-1) to (B-13-4) .

Regarding the addition amount ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin 1, the diamine component is preferably 0.9 to 1.1 mol relative to 1 mol of the tetracarboxylic acid component.

In addition, in addition to the aforementioned tetracarboxylic acid component and diamine component, an end-capping agent may also be used in the production of the polyimide resin 1. The blocking agent is preferably monoamine or dicarboxylic acid. The amount of the introduced end-capping agent is preferably 0.0001 to 0.1 mol relative to 1 mol of the tetracarboxylic acid component, and particularly preferably 0.001 to 0.06 mol. As monoamine blocking agents, for example, recommended: methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3- Methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. Among these, benzylamine and aniline can be preferably used. The dicarboxylic acid end-capping agent is preferably a dicarboxylic acid, and a part of the ring can be closed. For example, recommended: phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone two Carboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc. Among these, phthalic acid and phthalic anhydride can be preferably used.

The method of reacting the said tetracarboxylic acid component and a diamine component is not specifically limited, A well-known method can be used. Specific reaction methods include the following methods: (1) Add the tetracarboxylic acid component, the diamine component, and the reaction solvent to the reactor, stir at room temperature to 80°C for 0.5 to 30 hours, and then raise the temperature And carry out the imidization reaction; (2) After adding the diamine component and the reaction solvent to the reactor to dissolve, add the tetracarboxylic acid component, if necessary, stir at room temperature to 80°C for 0.5 to 30 hours, and then raise the temperature And carry out the imidization reaction; (3) add the tetracarboxylic acid component, the diamine component, and the reaction solvent into the reactor, immediately raise the temperature and carry out the imidization reaction.

The reaction solvent used in the production of the polyimide resin 1 may be one that does not hinder the imidization reaction and can dissolve the produced polyimide resin. For example, aprotic solvents, phenolic solvents, ether solvents, carbonate solvents, etc. can be mentioned.

Specific examples of aprotic solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, Amine-based solvents such as 1,3-dimethylimidazolidinone and tetramethylurea; lactone-based solvents such as γ-butyrolactone and γ-valerolactone; hexamethylphosphamide, hexamethylphosphine three Phosphorus-containing amine-based solvents such as amide; sulfur-containing solvents such as dimethyl sulfide, dimethyl sulfide, and cyclobutane; ketone-based solvents such as acetone, cyclohexanone, and methylcyclohexanone; picoline , Amine solvents such as pyridine; Ester solvents such as acetic acid (2-methoxy-1-methylethyl), etc.

Specific examples of phenolic solvents include: phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol, etc. Specific examples of ether solvents include: 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, Bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane and the like. In addition, specific examples of carbonate-based solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like. Among the above-mentioned reaction solvents, an amide-based solvent or a lactone-based solvent is preferable. Moreover, the said reaction solvent can be used individually or in mixture of 2 or more types.

Regarding the imidization reaction, it is preferable to perform the reaction while removing the water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the rate of imidization can be further improved.

In the above-mentioned imidation reaction, a well-known imidation catalyst can be used. Examples of the imidization catalyst include alkali catalysts and acid catalysts. Examples of base catalysts include: pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, and triethyl Amine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline and other organic base catalysts; potassium hydroxide, sodium hydroxide, potassium carbonate, Sodium carbonate, potassium bicarbonate, sodium bicarbonate and other inorganic base catalysts. Also, acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, and p-toluenesulfonic acid. , Naphthalenesulfonic acid, etc. The above-mentioned imidization catalysts can be used alone or in combination of two or more kinds. Among the above, considering the operability, it is preferable to use an alkali catalyst, an organic alkali catalyst is more preferable, and triethylamine is even more preferable, and a combination of triethylamine and triethylenediamine is particularly preferable.

The temperature of the imidization reaction is preferably 120 to 250°C, and more preferably 160 to 200°C in consideration of the reaction rate and inhibition of gelation. In addition, the reaction time is preferably 0.5 to 10 hours after the start of the distillation of the produced water.

The solid content concentration during the imidization reaction is preferably 30-60% by mass, more preferably 35-58% by mass, particularly preferably 40-56% by mass. If the solid content concentration during the imidization reaction is within this range, the imidization reaction proceeds well, and the water generated during the reaction is easily removed, so the degree of polymerization and the imidization rate can be improved. However, the solid content concentration during the imidization reaction is a value calculated from the following formula based on the mass of the tetracarboxylic acid component added to the reaction system, the diamine component in the reaction system, and the reaction solvent. Solid content concentration during the imidization reaction (mass %) = (total mass of tetracarboxylic acid component and diamine component)/(total mass of tetracarboxylic acid component, diamine component, and reaction solvent)×100

In addition, another preferred example of the polyimide resin that can be used in the present invention is shown, but the present invention is not limited to this.

[Polyimine resin 2] Polyimine resin 2 has structural unit A2 derived from tetracarboxylic dianhydride and structural unit B2 derived from diamine, and structural unit A2 contains a compound derived from the following formula (a-21) The structural unit (A-21) and the structural unit (A-22) derived from the compound represented by the following formula (a-22), and the structural unit B2 contains the structural unit (B-) derived from the compound represented by the following formula (b-21) 21) The ratio of the constituent unit (B-21) in the constituent unit B2 is 70 mol% or more. [化5]

＜Construction unit A2＞ The structural unit A2 is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin 2, and contains a structural unit (A-21) derived from the compound represented by the formula (a-21), and a structural unit derived from the formula (a- 22) The structural unit of the compound represented by (A-22). The compound represented by the formula (a-21) is the same as the compound represented by the above formula (a-11). In addition, the compound represented by the formula (a-22) is the same as the compound represented by the above formula (a-12). Since the structural unit A2 contains both the structural unit (A-21) and the structural unit (A-22), the colorless transparency, optical isotropy, and chemical resistance of the film can be improved. The structural unit (A-21) particularly contributes to the improvement of colorless transparency and optical isotropy, and the structural unit (A-22) particularly contributes to the improvement of chemical resistance.

The ratio of the constituent unit (A-21) in the constituent unit A2 is preferably 5 to 95 mol%, more preferably 15 to 95 mol%, still more preferably 20 to 90 mol%, particularly preferably 50 to 90 Mol%. The ratio of the constituent unit (A-22) in the constituent unit A2 is preferably 5 to 95 mol%, more preferably 5 to 85 mol%, still more preferably 10 to 80 mol%, particularly preferably 10 to 50 Mol%. The total ratio of the constituent units (A-21) and (A-22) in the constituent unit A2 is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, especially preferred It is more than 99 mol%. The upper limit of the total ratio of the structural units (A-21) and (A-22) is not particularly limited, and it is 100 mol%. The structural unit A2 may consist of only the structural unit (A-21) and the structural unit (A-22).

The structural unit A2 may contain structural units other than the structural units (A-21) and (A-22). The tetracarboxylic dianhydride that provides such a structural unit is not particularly limited, and examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 9,9'-bis (3,4-Dicarboxyphenyl) dianhydride, and 4,4'-(hexafluoroisopropylene) diphthalic anhydride and other aromatic tetracarboxylic dianhydrides (except, formula (a-22 ) Except for the compounds indicated); 1,2,3,4-cyclobutanetetracarboxylic dianhydride and norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane -5,5'',6,6''-tetracarboxylic dianhydride and other alicyclic tetracarboxylic dianhydrides (except for the compound represented by formula (a-21)); and 1,2,3,4 -Aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride. The structural unit arbitrarily contained in the structural unit A2 (that is, the structural unit other than the structural units (A-21) and (A-22)) may be one type or two or more types.

＜Construction unit B2＞ The structural unit B2 is a structural unit derived from a diamine that occupies in the polyimide resin, and contains a structural unit (B-21) derived from the compound represented by the formula (b-21). The compound represented by the formula (b-21) is the same as the compound represented by the above formula (b-11). Since the constituent unit B2 contains the constituent unit (B-21), the optical isotropy and chemical resistance of the film can be improved.

The ratio of the constituent unit (B-21) in the constituent unit B2 is 70 mol% or more. The ratio is preferably 75 mol% or more, more preferably 80 mol% or more. The upper limit of the ratio of the constituent unit (B-21) may be 90 mol%, 95 mol%, 99 mol%, or 100 mol%. The structural unit B2 may be composed of only the structural unit (B-21).

The structural unit B2 may contain structural units other than the structural unit (B-21). The diamine that provides such a structural unit is not particularly limited, and examples include 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2'-Dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl ether, 4,4' -Diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylaniline , 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, α,α'-bis(4-aminophenyl) )-1,4-Diisopropylbenzene, N,N'-bis(4-aminophenyl)p-xylylenedimethamide, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 9,9- Aromatic diamines such as bis(4-aminophenyl) pyridium and 4,4'-diamino-2,2'-bistrifluoromethyldiphenyl ether (except that the formula (b-21) represents Compounds except); 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane and other alicyclic diamines; and ethylenediamine and hexamethylenediamine Aliphatic diamines such as amines. The structural unit arbitrarily contained in the structural unit B2 (that is, the structural unit other than the structural unit (B-21)) may be one type or two or more types.

式(b-22-2)中，R各自獨立地為氫原子、氟原子或甲基。As the diamine providing the structural unit optionally contained in the structural unit B2, a compound represented by the following formula (b-22-1), a compound represented by the following formula (b-22-2), or the following formula (b-22- The compound represented by 3) and the compound represented by the following formula (b-22-4) are preferable. That is, in the polyimide resin of one aspect of the present invention, the structural unit B2 preferably further contains the structural unit (B-22), and the structural unit (B-22) is selected from the following formula (b-22- 1) The structural unit of the compound represented by (B-22-1), the structural unit (B-22-2) derived from the compound represented by the following formula (b-22-2), the structural unit derived from the following formula (b-22-3) At least one of the constituent unit (B-22-3) of the compound represented and the group consisting of the constituent unit (B-22-4) derived from the compound represented by the following formula (b-22-4). [化6]

In formula (b-22-2), R is each independently a hydrogen atom, a fluorine atom, or a methyl group.

The compound represented by the formula (b-22-1) is the same as the compound represented by the above formula (b-13-1). Since the constituent unit B contains the constituent unit (B-22-1), the colorlessness and transparency of the film can be improved.

The compound represented by the formula (b-22-2) is the same as the compound represented by the above formula (b-13-2), and the preferred range is also the same. Since the constituent unit B2 contains the constituent unit (B-22-2), the optical isotropy and heat resistance of the film can be improved.

The compound represented by the formula (b-22-3) is the same as the compound represented by the above formula (b-13-3). Since the constituent unit B2 contains the constituent unit (B-22-3), the colorlessness and transparency of the film can be improved.

The compound represented by the formula (b-22-4) is the same as the compound represented by the above formula (b-13-4). Since the constituent unit B2 contains the constituent unit (B-22-4), the colorlessness, transparency, chemical resistance, and mechanical properties of the film can be improved.

When the structural unit B2 contains the structural unit (B-21) and the structural unit (B-22), the ratio of the structural unit (B-21) in the structural unit B2 is preferably 70 to 95 mol%, more preferably 75 to 95 Mole%, and more preferably 75-90 mole%, the ratio of the constituent unit (B-22) in the constituent unit B2 is preferably 5-30 mole%, more preferably 5-25 mole%, and more Preferably, it is 10-25 mol%. The total ratio of the constituent unit (B-21) and the constituent unit (B-22) in the constituent unit B2 is preferably 75 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, Particularly preferred is 99 mol% or more. The upper limit of the total ratio of the structural unit (B-21) and the structural unit (B-22) is not particularly limited, and it is 100 mol%. The structural unit B may consist of only the structural unit (B-21) and the structural unit (B-22).

The structural unit (B-22) may be only the structural unit (B-22-1), or only the structural unit (B-22-2), or only the structural unit (B-22-3), or It can be only the constituent unit (B-22-4). In addition, the structural unit (B-22) may be a combination of two or more structural units selected from the group consisting of the structural units (B-22-1) to (B-22-4).

The number average molecular weight of the polyimide resin 2 is preferably 5,000 to 200,000 in view of the mechanical strength of the obtained polyimide film.

The polyimide resin 2 may contain a structure other than a polyimine chain (a structure in which the structural unit A2 and the structural unit B2 form an amide bond). Examples of structures other than the polyimine chain that can be contained in the polyimide resin include structures containing an amide bond. The polyimide resin 2 preferably contains a polyimine chain (a structure in which the constituent unit A2 and the constituent unit B2 form an imine bond) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin 2 is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 99% by mass or more.

[Manufacturing method of polyimide resin 2] The polyimide resin can be made of a tetracarboxylic acid component containing a compound providing the above-mentioned structural unit (A-21) and a compound providing the above-mentioned structural unit (A-22), and a tetracarboxylic acid component containing 70 mol% or more. It is produced by reacting the diamine component of the compound of the unit (B-21).

The compound providing the structural unit (A-21) may be a compound represented by the formula (a-21), but it is not limited to this, and its derivatives may also be provided within the scope of providing the same structural unit. The derivative can be exemplified by the tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-21) (that is, 1,2,4,5-cyclohexanetetracarboxylic acid) and the alkane of the tetracarboxylic acid Base ester. The compound providing the constituent unit (A-21) is preferably a compound represented by formula (a-21) (that is, dianhydride). Similarly, the compound providing the constitutional unit (A-22) includes a compound represented by the formula (a-22), but it is not limited to this, and its derivatives may also be provided within the scope of providing the same constitutional unit. Examples of the derivative include tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by formula (a-22) and alkyl esters of the tetracarboxylic acid. The compound providing the constituent unit (A-22) is preferably a compound represented by formula (a-22) (that is, dianhydride).

The tetracarboxylic acid component preferably contains 5-95 mol% of the compound providing the constituent unit (A-21), more preferably 15-95 mol%, still more preferably 20-90 mol%, particularly preferably 50- 90 mol%. The tetracarboxylic acid component preferably contains 5-95 mol% of the compound providing the constituent unit (A-22), more preferably 5-85 mol%, still more preferably 10-80 mol%, particularly preferably 10-80 mol%. 50 mol%. The total tetracarboxylic acid component preferably contains more than 50 mole% of the compound providing the structural unit (A-21) and the compound providing the structural unit (A-22), more preferably 70 mole% or more, and more preferably 90 mole% Ear% or more, particularly preferably 99 mol% or more. The upper limit of the total content ratio of the compound providing the structural unit (A-21) and the compound providing the structural unit (A-22) is not particularly limited, and is 100 mol%. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A-21) and the compound providing the structural unit (A-22).

The tetracarboxylic acid component may also include compounds other than the compound providing the constituent unit (A-21) and the compound providing the constituent unit (A-22). Examples of the compound include the above-mentioned aromatic tetracarboxylic dianhydride and alicyclic tetracarboxylic acid Acid dianhydride, aliphatic tetracarboxylic dianhydride, and their derivatives (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.). The compound arbitrarily contained in the tetracarboxylic acid component (that is, a compound other than the compound providing the structural unit (A-21) and the compound providing the structural unit (A-22)) may be one type or two or more types.

The compound providing the structural unit (B-21) may be a compound represented by the formula (b-21), but it is not limited thereto, and its derivatives may also be provided within the scope of providing the same structural unit. Examples of the derivative include diisocyanates corresponding to the diamine represented by formula (b-21). The compound providing the constituent unit (B-21) is preferably a compound represented by the formula (b-21) (that is, a diamine).

The diamine component contains more than 70 mol% of the compound providing the constituent unit (B-21). The diamine component preferably contains 75 mol% or more of the compound providing the constituent unit (B-21), more preferably 80 mol% or more. The upper limit of the content ratio of the compound providing the constituent unit (B-21) may be 90 mol%, 95 mol%, 99 mol%, or 100 mol%. The diamine component may be composed only of the compound providing the structural unit (B-21).

The diamine component may also include a compound other than the compound providing the constituent unit (B-21). The compound may include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and their derivatives (diisocyanate Wait). The compound arbitrarily contained in the diamine component (that is, the compound other than the compound providing the structural unit (B-21)) may be one type or two or more types.

The compound arbitrarily contained in the diamine component is preferably a compound that provides the structural unit (B-22) (that is, a compound that provides the structural unit (B-22-1), a compound that provides the structural unit (B-22-2), Provide the compound of the structural unit (B-22-3), and provide the compound of the structural unit (B-22-4)). The compound that provides the constituent unit (B-22) can include the compound represented by the formula (b-22-1), the compound represented by the formula (b-22-2), the compound represented by the formula (b-22-3), and the formula The compound represented by (b-22-4) is not limited thereto, and may be a derivative thereof within the range that can form the same structural unit. Examples of the derivative include diisocyanates corresponding to the diamines represented by formulas (b-22-1) to (b-22-4). The compound providing the constituent unit (B-22) is preferably a compound represented by formula (b-22-1) to formula (b-22-4) (that is, diamine).

When the diamine component contains the compound providing the structural unit (B-21) and the compound providing the structural unit (B-22), the diamine component preferably contains 70-95 mole% of the compound providing the structural unit (B-21), More preferably 75-95 mol%, still more preferably 75-90 mol%, preferably containing 5-30 mol% of the compound providing the constituent unit (B-22), more preferably 5-25 mol% , And more preferably 10-25 mol%. The total diamine component should preferably contain 75 mol% or more of the compound providing the structural unit (B-21) and the compound providing the structural unit (B-22), more preferably 80 mol% or more, and more preferably 90 mol% % Or more, particularly preferably 99 mol% or more. The upper limit of the total content ratio of the compound providing the structural unit (B-21) and the compound providing the structural unit (B-22) is not particularly limited, and that is, it is 100 mol%. The diamine component may be composed of only the compound providing the structural unit (B-21) and the compound providing the structural unit (B-22).

The compound providing the structural unit (B-22) can only be the compound providing the structural unit (B-22-1), or only the compound providing the structural unit (B-22-2), or only the structural unit can be provided The compound of (B-22-3) may also only provide the compound of the constituent unit (B-22-4). In addition, the compound providing the structural unit (B-22) may also be a combination of two or more compounds selected from the group consisting of the compounds providing the structural unit (B-22-1) to (B-22-4) .

Regarding the addition amount ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin 2, the diamine component is preferably 0.9 to 1.1 mol relative to 1 mol of the tetracarboxylic acid component.

In addition, in addition to the aforementioned tetracarboxylic acid component and diamine component, an end-capping agent may also be used in the production of the polyimide resin 2. The blocking agent is as described with respect to the polyimide resin 1, and the preferred range is also the same.

The method of reacting the said tetracarboxylic acid component and a diamine component is not specifically limited, A well-known method can be used. The specific reaction method is as described with respect to polyimide resin 1.

The reaction solvent used in the production of the polyimide resin 2 may be one that does not hinder the imidization reaction and can dissolve the polyimide produced. The specific example of the reaction solvent is described with respect to the polyimide resin 1, and the preferred range is also the same.

Regarding the imidization reaction, it is preferable to perform the reaction while removing the water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the rate of imidization can be further improved.

In the above-mentioned imidation reaction, a well-known imidation catalyst can be used. Regarding the specific example of the imidization catalyst, as explained about the polyimide resin 1, the preferable range is also the same.

The temperature of the imidization reaction is preferably 120 to 250°C, and more preferably 160 to 200°C in consideration of the reaction rate and inhibition of gelation. In addition, the reaction time is preferably 0.5 to 10 hours after the start of the distillation of the produced water.

In addition, as another preferable example of the polyimide resin that can be used in the present invention, a polyimide resin obtained from the following copolymers can also be exemplified, but the present invention is not limited to this.

[Copolymer 3] Copolymer 3 is a copolymer having structural unit A3 derived from tetracarboxylic dianhydride and structural unit B3 derived from diamine, The constituent unit A3 consists of a constituent unit (A-31) derived from alicyclic tetracarboxylic dianhydride (a-31), and a tetracarboxylic dianhydride (A-31) derived from alicyclic tetracarboxylic dianhydride (a-31) a-32) constitute the unit (A-32), The structural unit B3 contains the structural unit (B-31) derived from the compound represented by the following formula (b-31), The structural unit (A-32) contains a structural unit selected from the structural unit (A-32-1) derived from the compound represented by the following formula (a-32-1), and the structural unit derived from the compound represented by the following formula (a-32-2) (A-32-2), the structural unit (A-32-3) derived from the compound represented by the following formula (a-32-3), and the structural unit (A-32-3) derived from the compound represented by the following formula (a-32-4) A-32-4) At least 1 of the group constituted, The copolymer has an imine repeating structural unit formed by a compound providing the constituent unit (A-31) and a compound providing the constituent unit (B-31), and has a compound that provides the constituent unit (A-32) and a compound providing the constituent unit (A-32). A repeating structural unit of amide acid formed by the compound constituting unit B3.

[化7]

＜Construction unit A3＞ The constituent unit A3 is a constituent unit derived from tetracarboxylic dianhydride in copolymer 3, consisting of constituent unit (A-31) derived from alicyclic tetracarboxylic dianhydride (a-31), and a constituent unit derived from alicyclic dianhydride (a-31). It is composed of the structural unit (A-32) of tetracarboxylic dianhydride (a-32) other than tetracarboxylic dianhydride (a-31).

The structural unit (A-31) is a structural unit derived from alicyclic tetracarboxylic dianhydride (a-31). Considering the viewpoints of high transparency, high heat resistance, and low residual stress, the structural unit (A-31) preferably contains the structural unit (A-31-1) derived from the compound represented by the following formula (a-31-1). The compound represented by the formula (a-31-1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6'' -Tetracarboxylic dianhydride.

[化8]

The ratio of the constituent unit (A-31-1) in the constituent unit (A-31) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, particularly preferably More than 99 mol%. The upper limit of the ratio is not particularly limited, that is, 100 mol%. The structural unit (A-31) may have a structural unit derived from alicyclic tetracarboxylic dianhydride other than the compound represented by the formula (a-31-1). Examples of the alicyclic tetracarboxylic dianhydride include: 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2, 4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, etc. The alicyclic tetracarboxylic dianhydride (a-31) may be one type alone or two or more types may be combined.

The structural unit (A-32) is a structural unit derived from tetracarboxylic dianhydride (a-32) other than alicyclic tetracarboxylic dianhydride (a-31). The tetracarboxylic dianhydride (a-32) includes one or more selected from the group consisting of aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides, and it is preferable to include aromatic tetracarboxylic dianhydrides. That is, the structural unit (A-32) preferably contains a structural unit derived from aromatic tetracarboxylic dianhydride. Considering the viewpoints of high heat resistance and low residual stress, the structural unit (A-32) contains the structural unit (A-32-1) selected from the compound represented by the following formula (a-32-1), and the structural unit (A-32-1) from the following formula ( a-32-2) the structural unit (A-32-2) of the compound represented by the following formula (a-32-3), the structural unit (A-32-3) from the compound represented by the following formula (a-32-3), and the structural unit (A-32-3) from the compound represented by the following formula (a -32-4) represents at least one of the group consisting of the structural unit (A-32-4) of the compound.

[化9]

The compound represented by the formula (a-32-1) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include: 3,3',4,4'- represented by the following formula (a-32-1s) Biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a-32-1a), the following formula (a-32-1a) a-32-1i) represents 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BPDA). Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a-32-1s) is preferable.

[化10]

The compound represented by the formula (a-32-2) is p-phenylene bis(trimellitic acid ester) dianhydride (TAHQ).

The compound represented by the formula (a-32-3) is oxydiphthalic anhydride (ODPA). Specific examples of the compound represented by the following formula (a-32-3s) are 4,4'-oxydiphthalic anhydride (ODPA) Phthalic anhydride (s-ODPA), 3,4'-oxydiphthalic anhydride (a-ODPA) represented by the following formula (a-32-3a), represented by the following formula (a-32-3i) Of 3,3'-oxydiphthalic anhydride (i-ODPA). Among them, it is preferably 4,4'-oxydiphthalic anhydride (s-ODPA) represented by the following formula (a-32-3s).

[化11]

The compound represented by formula (a-32-4) is pyromellitic dianhydride (PMDA).

Considering high heat resistance and low residual stress, the structural unit (A-32) should contain at least one selected from the group consisting of structural unit (A-32-1) and structural unit (A-32-2) . The structural unit (A-32-1) is better in terms of improving the heat resistance and thermal stability of the film, and further reducing the residual stress, and the structural unit (A-32-2) is in terms of lowering YI and more excellent colorless transparency. Department is better.

Tetracarboxylic dianhydride (a-32) may contain tetracarboxylic dianhydrides other than the compounds represented by formulas (a-32-1) to (a-32-4). The tetracarboxylic dianhydride may include: 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3, 3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, and represented by the following formula (a-32-5) Aromatic tetracarboxylic dianhydrides such as compounds; and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. Among these, aromatic tetracarboxylic dianhydride is preferable. The tetracarboxylic dianhydride (a-32) may be one type alone or two or more types may be combined.

[化12]

The ratio of the structural unit (A-32-1) to the structural unit (A-32-4) in the structural unit (A-32) is preferably 45 mol% or more, more preferably 70 mol% or more, and more preferably It is 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited, that is, 100 mol%. The structural unit (A-32) only needs to contain at least one selected from the structural unit (A-32-1) to the structural unit (A-32-4), and it may only be selected from the structural unit (A-32 -1) Any one of the constituent units (A-32-4). When the structural unit (A-32) contains two or more structural units selected from the structural unit (A-32-1) to the structural unit (A-32-4), each structure in the structural unit (A-32) The ratio of the units is not particularly limited, and can be set to any ratio.

The molar ratio of the constituent unit (A-31) and the constituent unit (A-32) in the constituent unit A3 [(A-31)/(A-32)], preferably 10/90～90/10, more preferably It is 30/70 to 85/15, and more preferably 50/50 to 80/20. The ratio of the structural unit derived from the aromatic tetracarboxylic dianhydride in the structural unit (A-32) is preferably 45 mol% or more, more preferably 60 mol% or more, and still more preferably 85 mol% or more. The upper limit of the total content ratio is not particularly limited, and that is, it is 100 mol%.

＜Construction unit B3＞ The structural unit B3 is a structural unit derived from a diamine in the copolymer of the present invention, and contains a structural unit (B-31) derived from a compound represented by the following formula (b-31). Since the structural unit B3 contains the structural unit (B-31), the transparency is excellent, and low residual stress and low retardation characteristics can be achieved at the same time.

[化13]

The compound represented by the formula (b-31) is the same as the compound represented by the above formula (b-13-1).

The structural unit B3 preferably further contains the structural unit (B-32) derived from the compound represented by the following general formula (b-32). Since the structural unit B3 contains the structural unit (B-32), the residual stress is reduced.

[化14]

In formula (b-32), Z ¹ and Z ² each independently represent a divalent aliphatic group or a divalent aromatic group, and R ¹ and R ² each independently represent a monovalent aromatic group or a monovalent aliphatic group R ³ and R ⁴ each independently represent a monovalent aliphatic group, R ⁵ and R ⁶ each independently represent a monovalent aliphatic group or a monovalent aromatic group, and m and n each independently represent an integer of 1 or more , The sum of m and n represents an integer from 2 to 1000. However, ^{at least one of R 1} and R ² represents a monovalent aromatic group. In addition, in formula (b-32), two or more different repeating units described side by side with [] can be repeated in any form and order of random, alternating, or block.

In the formula (b-32), the divalent aliphatic group or the divalent aromatic group ^{in Z 1} and Z ^{2 may be substituted with a fluorine atom.} Examples of the divalent aliphatic group include a divalent saturated or unsaturated aliphatic group having 1 to 20 carbon atoms. The carbon number of the divalent aliphatic group is preferably 3-20. Examples of the divalent saturated aliphatic group include alkylene groups having 1 to 20 carbon atoms, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, and octamethylene. Methyl, decamethylene, dodecamethylene, etc. Examples of the divalent unsaturated aliphatic group include alkenylene groups having 2 to 20 carbon atoms, and examples include vinylene groups, propenylene groups, and alkylene groups having an unsaturated double bond at the end. Examples of the divalent aromatic group include arylene groups having 6 to 20 carbon atoms and aralkylene groups having 7 to 20 carbon atoms. Specific examples of the arylene groups having 6 to 20 carbon atoms in Z ¹ and Z ² include ortho-phenylene, meta-phenylene, para-phenylene, 4,4'-biphenylene, 2, 6-Naphthylene and so on. Z ¹ and Z ^{2 are} particularly preferably trimethylene and p-phenylene, and more preferably trimethylene.

In formula (b-32), ^{examples of the monovalent aliphatic group among R 1} to R ⁶ include monovalent saturated or unsaturated aliphatic groups. Examples of the monovalent saturated aliphatic group include alkyl groups having 1 to 22 carbon atoms, and examples include methyl, ethyl, and propyl groups. Examples of the monovalent unsaturated aliphatic group include alkenyl groups having 2 to 22 carbon atoms, and examples thereof include vinyl groups and propenyl groups. These groups may also be substituted by fluorine atoms. ^{Examples of the monovalent aromatic group in R 1} , R ² , R ⁵ and R ⁶ in the formula (b-32) include an aryl group having 6 to 20 carbons, and an aryl group substituted with an alkyl group having 7 to 30 carbons. Group, C7-30 aralkyl group, etc. The monovalent aromatic group is preferably an aryl group, more preferably a phenyl group. At least one of R ¹ and R ² represents a monovalent aromatic group, it is ^{preferable that both R 1} and R ² are monovalent aromatic groups, and it is more ^{preferable that both R 1 and R 2} are phenyl groups. R ³ and R ^{4 are} preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl groups. R ⁵ and R ^{6 are} preferably monovalent aliphatic groups, more preferably methyl.

In the formula (b-32), m represents the repeating number of siloxane units bonded to at least one monovalent aromatic group, and n represents the repeating number of siloxane units bonded to the monovalent aliphatic group. m and n each independently represent an integer of 1 or more, and the sum of m and n (m+n) represents an integer of 2 to 1000. The sum of m and n preferably represents an integer of 3 to 500, more preferably 3 to 100, and still more preferably an integer of 3 to 50. The ratio of m/n is preferably 50/50 to 99/1, more preferably 60/40 to 90/10, and still more preferably 70/30 to 80/20.

The functional group equivalent of the compound represented by formula (b-32) is preferably 150-5,000 g/mol, more preferably 400-4,000 g/mol, and still more preferably 500-3,000 g/mol. In addition, the functional group equivalent means the mass of the compound represented by the formula (b-32) per 1 mole of the functional group.

The content of the polyorganosiloxane unit is preferably 5 to 45% by mass, more preferably 7 to 40% by mass, and still more preferably 10 to 35% by mass relative to the total of the structural unit A3 and the structural unit B3. If the content of the polyorganosiloxane unit is within the aforementioned range, the low retardation value and the low residual stress can be balanced to a higher degree. The polyorganosiloxane unit has the same meaning as the structural unit (B-32). The content of the polyorganosiloxane unit relative to the total of the structural unit A3 and the structural unit B3 can be provided by the compound of the structural unit (B-32), It is preferable to calculate the mass ratio of the addition amount of the compound represented by the formula (b-32) to the total addition amount of the raw materials providing the constituent unit A3 and the constituent unit B3.

As commercially available products of the compound represented by formula (b-32), "X-22-9409" and "X-22-1660B-3" manufactured by Shin-Etsu Chemical Co., Ltd. can be cited.

The structural unit B3 preferably further contains the structural unit (B-33) derived from the compound represented by the following formula (b-33). [化15]

The compound represented by the formula (b-33) is the same as the compound represented by the above formula (b-13-2), and the preferred range is also the same. By containing the aforementioned structural unit (B-33), the copolymer of the present invention improves transparency and heat resistance.

The ratio of the constituent unit (B-31) in the constituent unit B3 is preferably 45 mol% or more, more preferably 48 mol% or more, still more preferably 85 mol% or more, and particularly preferably 88 mol% or more, It is preferably 100 mol% or less, more preferably 99.5 mol% or less, and still more preferably 99.0 mol% or less. The structural unit B3 may be composed of only the structural unit (B-31). When the structural unit B3 contains the structural unit (B-32), the ratio of the structural unit (B-32) in the structural unit B3 is preferably 0.01-15.0 mol%, more preferably 0.5-12.0 mol%, and still more preferably 1.0～8.0 mole%. When structural unit B3 contains structural unit (B-33), the ratio of structural unit (B-33) in structural unit B3, considering low residual stress, is preferably 5 mol% or more, more preferably 10 mol% Above, it is more preferably 25 mol% or more, preferably 65 mol% or less, more preferably 55 mol% or less, and still more preferably 50 mol% or less. When the structural unit B3 contains the structural unit (B-33), the total ratio of the structural units (B-31) and (B-33) in the structural unit B3 is preferably 85.0-100 mol%, more preferably 88.0-99.5 mol% Ear%, and more preferably 92.0-99.0 mole%. When the structural unit B3 does not contain the structural unit (B-33), the ratio of the structural unit (B-31) in the structural unit B3 is also preferably in the same range as the above. The total content ratio of the structural units (B-31) to (B-33) in the structural unit B3 is preferably 45-100 mol%, more preferably 60-100 mol%, and still more preferably 85-100 mol% %, particularly preferably 100 mol%.

The structural unit B3 may contain structural units other than the structural units (B-31) to (B-33). The diamine that provides such a structural unit is not particularly limited, and examples include 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2'-Dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-Dimethylbiphenyl-4,4'- Diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl)-2-propyl] Benzene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminophenylidene aniline, 3,4'-di Amino diphenyl ether, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, α,α'-bis(4 -Aminophenyl)-1,4-dicumyl, N,N'-bis(4-aminophenyl)p-xylylenedimethamide, 4,4'-bis(4-aminophenoxy) Yl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane , 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 1,4-bis(4-aminophenoxy)benzene and other aromatic diamines; 1,3-bis( Alicyclic diamines such as aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine. The structural units other than the structural units (B-31) to (B-33) arbitrarily contained in the structural unit B3 may be one type or two or more types. The structural unit B3 preferably does not contain structural units other than the structural units (B-31) to (B-33). From the viewpoint of achieving a low retardation value, it is particularly preferable that the constituent unit B3 does not contain a constituent unit derived from 2,2'-bis(trifluoromethyl)benzidine.

<Amino acid repeating structure unit/Amino acid repeating structure unit> Copolymer 3 has an imine repeating structural unit formed from a compound providing the structural unit (A-31) and a compound providing the structural unit (B-31), and a compound providing the structural unit (A-32) and providing composition A repeating structural unit of amide acid formed by the compound of unit B3. Copolymer 3 may also have an imine repeating structural unit formed by a compound other than the compound providing the structural unit (A-31) and the compound providing the structural unit B3, and a compound providing the structural unit (A-31) and the provided structure Unit (B-31) is a repeating structural unit formed by compounds other than the compound of the unit (B-31). Similarly, the copolymer 3 may have a repeating structural unit of amide formed from a compound other than the compound providing the structural unit (A-32) and the compound providing the structural unit B3.

[Manufacturing method of copolymer 3] Copolymer 3 can be made up of a tetracarboxylic acid component composed of a compound providing a structural unit (A-31) and a compound providing a structural unit (A-32), and a composition containing a structural unit (B-31). The diamine component of the compound of unit B3 is produced by reaction, and it is preferably produced by the method having the following steps 1 and 2. Step 1: A step of reacting the compound providing the structural unit (A-31) with the compound providing the structural unit (B-31) to obtain an oligomer having an imine repeating structural unit. Step 2: The oligomer obtained in step 1, the compound providing the structural unit (A-32), and the compound providing the structural unit B3 are reacted to obtain a copolymer having an imine repeating structural unit and an amide repeating structural unit物3的Steps. By using the manufacturing method having the aforementioned steps 1 and 2, it is possible to manufacture the copolymer 3 capable of forming a film with excellent colorless transparency and heat resistance, low retardation value and low residual stress. Hereinafter, the manufacturing method of the copolymer 3 is demonstrated.

＜Tetracarboxylic acid component＞ The compound providing the structural unit (A-31) includes alicyclic tetracarboxylic dianhydride (a-31), but it is not limited to this, and its derivatives may be provided within the range of providing the same structural unit. Examples of the derivative include alicyclic tetracarboxylic acid corresponding to alicyclic tetracarboxylic dianhydride (a-31) and alkyl esters of the alicyclic tetracarboxylic acid. The compound providing the constituent unit (A-31) is preferably an alicyclic tetracarboxylic dianhydride (a-31). Similarly, the compound providing the constitutional unit (A-32) includes tetracarboxylic dianhydride (a-32), but it is not limited to this, and its derivatives may also be provided within the scope of providing the same constitutional unit. Examples of the derivative include tetracarboxylic acid corresponding to tetracarboxylic dianhydride (a-32) and alkyl esters of the tetracarboxylic acid. The compound providing the constituent unit (A-32) is preferably tetracarboxylic dianhydride (a-32).

The molar ratio of the compound providing the constituent unit (A-31) to the compound providing the constituent unit (A-32) in the tetracarboxylic acid component [(A-31)/(A-32)], preferably 10/90 ～90/10, more preferably 30/70～85/15, still more preferably 50/50～80/20.

The compound providing the structural unit (A-31) is preferably a compound providing the structural unit (A-31-1). The ratio of the compound providing the constituent unit (A-31-1) in the compound providing the constituent unit (A-31) is preferably 45 mol% or more, more preferably 70 mol% or more, and more preferably 90 mol% % Or more, particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited, that is, 100 mol%. As far as the compound providing the structural unit (A-32) is concerned, it is preferably selected from the group consisting of the compound providing the structural unit (A-32-1), the compound providing the structural unit (A-32-2), and the compound providing the structural unit (A-32-2). One or more of the group consisting of the compound of 32-3) and the compound providing the constituent unit (A-32-4). The total ratio of the compound providing the structural unit (A-32-1) to the structural unit (A-32-4) in the compound providing the structural unit (A-32) is preferably 45 mol% or more, more preferably 70 mol% Ear% or more, more preferably 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may also include providing structural unit (A-31-1), structural unit (A-32-1), structural unit (A-32-2), structural unit (A-32-3), and The compound other than the compound of the structural unit (A-32-4) may be one type or two or more types.

＜Diamine component＞ The compound providing the structural unit B3 includes diamine, but it is not limited thereto, and its derivatives may also be provided within the scope of providing the same structural unit. Examples of the derivatives include diisocyanates corresponding to diamines. The compound providing the building block B3 is preferably a diamine. The compound providing the constituent unit (B-31) is preferably a compound represented by the formula (b-31) (that is, a diamine). Similarly, the compound providing the constituent unit (B-32) is preferably a compound represented by the general formula (b-32) (that is, diamine), and the compound providing the constituent unit (B-33) is preferably a compound represented by the formula (b- 33) The compound represented by (ie, diamine).

The diamine component preferably contains 45 mol% or more of the compound providing the constituent unit (B-31), more preferably 48 mol% or more, more preferably 85 mol% or more, and particularly preferably 88 mol% or more, It is preferable to contain 100 mol% or less, more preferably 99.5 mol% or less, and still more preferably 99.0 mol% or less. The diamine component may be composed only of the compound providing the structural unit (B-31). When the diamine component contains the compound providing the structural unit (B-32), the total diamine component preferably contains 0.01-15.0 mol% of the compound providing the structural unit (B-32), more preferably 0.5-12.0 mol% , And more preferably 1.0～8.0 mol%. When the diamine component contains a compound that provides the constituent unit (B-33), the total diamine component preferably contains 5 to 65 mol% of the compound that provides the constituent unit (B-33), more preferably 10 to 55 mol% , And more preferably 25-50 mol%. The diamine component may also be a combination of a compound providing structural unit (B-31), and one or more compounds selected from a compound providing structural unit (B-32) and a compound providing structural unit (B-33).

The total content ratio of the compound providing the structural unit (B-31), the compound providing the structural unit (B-32), and the compound providing the structural unit (B-33) is preferably 45 mol% in all diamine components Above, more preferably 60 mol% or more, and still more preferably 85 mol% or more. The upper limit of the total content ratio is not particularly limited, and that is, it is 100 mol%.

The diamine component may also include a compound providing the building block (B-31), a compound providing the building block (B-32), and a compound providing the building block (B-33) other than the compound providing the building block B3, such compounds Examples include the above-mentioned aromatic diamines, alicyclic diamines, and aliphatic diamines, and their derivatives (diisocyanates, etc.). The compound other than the compound providing the structural unit (B-31) to (B-33) arbitrarily included in the diamine component may be one type or two or more types.

Regarding the addition amount ratio of the tetracarboxylic acid component and the diamine component used in the manufacture of the copolymer 3, the diamine component is preferably 0.9 to 1.1 mol relative to 1 mol of the tetracarboxylic acid component.

＜Solvent＞ The solvent used in the manufacture of copolymer 3 may be any solvent that can dissolve the resulting copolymer. The specific example of the reaction solvent is described with respect to the polyimide resin 1. Among the above-mentioned reaction solvents, amide-based solvents or lactone-based solvents are preferred, amide-based solvents are more preferred, and N-methyl-2-pyrrolidone is particularly preferred. The above-mentioned reaction solvents can be used alone or in combination of two or more kinds.

<Step 1> Step 1 is a step of reacting a compound providing structural unit (A-31) with a compound providing structural unit (B-31) to obtain an oligomer having an imine repeating structural unit. When the tetracarboxylic acid component used in step 1 contains a compound that provides the structural unit (A-31), and the structural unit (A-31) contains the structural unit (A-31-1), it is appropriate to use the provided structural unit in step 1. (A-31-1) The total amount of compounds. The diamine component used in step 1 includes a compound that provides the structural unit (B-31), and may also contain diamine components other than the compound that provides the structural unit (B-31) within the range that does not impair the effect of the present invention . Such a compound can be exemplified by a compound providing the constituent unit (B-33). Regarding the addition amount ratio of the components used in step 1, relative to the compound providing the constituent unit (A-31), the diamine component used in step 1 is preferably 0.9-1.1 mol, more preferably 1.0-1.1 mol good.

The method of reacting the tetracarboxylic acid component containing the compound providing the constituent unit (A-31) with the diamine component containing the compound providing the constituent unit (B-31) to obtain the oligomer is not particularly limited , Well-known methods can be used. The specific reaction method is as described with respect to polyimide resin 1.

In the above-mentioned imidation reaction, a well-known imidation catalyst can be used. Specific examples of the imidization catalyst are described with respect to polyimide resin 1, and the preferred range is also the same.

The temperature of the imidization reaction is preferably 120 to 250°C, and more preferably 160 to 200°C in consideration of the reaction rate and inhibition of gelation. In addition, the reaction time is preferably 0.5 to 10 hours after the start of the distillation of the produced water.

The oligomer obtained in step 1 has an imine repeating structural unit formed of a compound providing the constitutional unit (A-31) and a compound providing the constitutional unit (B-31). The oligomer obtained in step 1 preferably has amine groups at both ends of the main chain of the molecular chain. Using the above method, a solution containing oligomers dissolved in a solvent can be obtained. The solution containing the oligomer obtained in step 1 may contain at least a part of the components used as the tetracarboxylic acid component and the diamine component in step 1 as an unreacted monomer within a range that does not impair the effects of the present invention. body.

<Step 2> Step 2 is to react the oligomer obtained in step 1, the compound providing the constituent unit (A-32), and the compound providing the constituent unit B3 to obtain a compound having an imine repeating structural unit and an amidic acid repeating structural unit Copolymer step. The tetracarboxylic acid component used in step 2 includes a compound providing the structural unit (A-32), and may also include a compound providing the structural unit (A-31) within a range that does not impair the effect of the present invention. However, the tetracarboxylic acid component used in step 2 should preferably not contain the compound that provides the structural unit (A-31-1). In addition, it is preferable to use the total amount of the compound providing the constituent unit (A-32) in step 2. The diamine component used in step 2 provides the compound constituting unit B3. The diamine component used in step 2 means the compound that provides the constituent unit B3 in the raw material monomer of the copolymer of the present invention except for the diamine component that constitutes the oligomer obtained in step 1. The unreacted diamine component remaining in the solution containing the oligomer obtained in step 1 can also be used as the diamine component in step 2. The diamine component used in step 2 preferably contains at least a compound that provides the constituent unit (B-31). When using the compound that provides the building block (B-32), it is advisable to use the total amount in step 2.

In step 2 to obtain the copolymer, the tetracarboxylic acid component containing the compound providing the constituent unit (A-32), the diamine component containing the compound providing the constituent unit B3, and the oligomer obtained in step 1 are reacted The method is not particularly limited, and a known method can be used. Specific reaction methods include the following methods: (1) The oligomer, tetracarboxylic acid component, diamine component, and solvent obtained in step 1 are added to the reactor at 0 to 120°C, preferably 5 to Stir at 80°C for 1 to 72 hours; (2) Add the oligomer, diamine component (preferably to the diamine component other than the compound of the constituent unit (B-32)) obtained in step 1, and the solvent After dissolving in the reactor, add the tetracarboxylic acid component, stir at the range of 0-120°C, preferably 5-80°C for 1 to 72 hours, and then add the supply constituent unit as the diamine component (B-32) The compound and solvent should be stirred at 0～120℃, preferably 15～80℃, for 0.5～10 hours. When the diamine component contains a compound that provides the structural unit (B-32), the above-mentioned production method (2) is suitable. When the reaction is performed below 80°C, the molecular weight of the copolymer obtained in step 2 will not vary depending on the temperature history during polymerization, and the progress of thermal imidization can be suppressed, so the copolymer can be produced stably Things.

Copolymer 3 is a copolymer with repeating structure units of amide acid and repeating structure units of amide. The copolymer is the tetracarboxylic acid component in step 2, the diamine component in step 2, and the oligomer obtained in step 1. The product of addition polymerization of polymers. Copolymer 3 has an imine repeating structural unit formed by the compound providing the constitutional unit (A-31) and the compound providing the constitutional unit (B-31) in step 1, and has the constitutional unit ( The compound of A-32) and the compound providing the constituent unit B3 form a repeating structural unit of amide acid.

Using the above method, a copolymer solution containing copolymer 3 dissolved in a solvent can be obtained. The concentration of the copolymer in the obtained copolymer solution is usually 1-50% by mass, preferably 3-35% by mass, more preferably 10-30% by mass.

The number average molecular weight of the copolymer 3, considering the mechanical strength of the obtained polyimide film, is preferably 5,000 to 500,000. Moreover, the number average molecular weight of the copolymer 3 can be calculated|required from the standard polymethyl methacrylate (PMMA) conversion value obtained by the gel filtration chromatography measurement, for example.

[Manufacturing method of polyimide film] The manufacturing method of the polyimide film of this invention is not specifically limited, A well-known method can be used. For example, a method of applying a polyimide varnish to a smooth support such as a glass plate, a metal plate, or plastic or forming into a film, and then heating the varnish to remove organic solvents such as reaction solvents and diluting solvents, etc. .

As the coating method of the varnish, well-known coating methods, such as spin coating, slit coating, and knife coating, are mentioned. Among them, slit coating can control the intermolecular alignment and improve chemical resistance, which is preferable from the viewpoint of workability. As a method of removing the organic solvent contained in the varnish by heating, it is suitable to evaporate the organic solvent at a temperature of 150°C or less to make it non-viscous, and then at a temperature above the boiling point of the organic solvent used (not particularly limited, 200-500°C) is preferably dried. Moreover, it is suitable to dry in an air environment or a nitrogen environment. The pressure of the dry environment may be any of reduced pressure, normal pressure, and increased pressure.

＜Polyimide varnish＞ Polyimide varnish is made by dissolving polyimide resin in organic solvent. That is, the polyimide varnish contains a polyimide resin and an organic solvent, and the polyimide resin is dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyimide resin. As the reaction solvent used in the production of the polyimide resin, the above-mentioned compounds are preferably used alone or in combination of two or more. The polyimide varnish may be the polyimide solution itself obtained by dissolving the polyimide resin obtained by the polymerization method in the reaction solvent, or it may be obtained by further adding a diluting solvent to the polyimide solution.

The above-mentioned polyimide resins 1 and 2 have solvent solubility, so they can be made into high-concentration varnishes that are stable at room temperature. The polyimide varnish preferably contains 5-40% by mass of polyimide resin 1 or 2, and more preferably contains 10-30% by mass. The viscosity of the polyimide varnish is preferably 1～200Pa･s, more preferably 1.5～100Pa･s, and even more preferably 2～100Pa･s. The viscosity of the polyimide varnish is a value measured at 25°C using an E-type viscometer. In addition, within the range that does not impair the required characteristics of the polyimide film, the polyimide varnish may also contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, and modifiers. Various additives such as leveling agent, defoaming agent, fluorescent whitening agent, crosslinking agent, polymerization initiator, sensitizer, etc. The manufacturing method of polyimide varnish is not specifically limited, A well-known method can be used.

＜Polyamide varnish＞ In addition, the polyimide film can also be manufactured using a polyimide varnish obtained by dissolving polyimide acid in an organic solvent. The polyimide contained in the aforementioned polyimide varnish is preferably a precursor of polyimide resin 1 or 2. Polyimide resin 1, which is the precursor of polyimide resin 1, contains a compound that provides the above-mentioned structural unit (A-11) and a tetracarboxylic acid component that provides the compound of the above-mentioned structural unit (A-12). The compound of the aforementioned structural unit (B-11) and the product of the addition polymerization reaction of the diamine component of the compound of the aforementioned structural unit (B-12). Polyimide resin 2 as the precursor of polyimide resin, contains the compound providing the above-mentioned structural unit (A-21) and the tetracarboxylic acid component of the compound providing the above-mentioned structural unit (A-22), and contains 70 Mole% or more provides the product of the addition polymerization reaction of the diamine component of the compound of the above-mentioned structural unit (B-21). By imidizing these polyimide acids (dehydration ring closure), polyimide resin 1 or 2 as the final product can be obtained. As the organic solvent contained in the polyimide varnish, the organic solvent contained in the polyimide varnish can be used. In the present invention, the polyamide varnish may be the polyamide solution itself obtained by the addition polymerization reaction of the tetracarboxylic acid component and the diamine component in the reaction solvent, or it may be the polyamide acid solution It is obtained by adding further dilution solvent.

The method of manufacturing a polyimide film using a polyamide varnish is not specifically limited, A well-known method can be used. For example, the polyamide varnish can be coated on a smooth support such as a glass plate, metal plate, plastic, or formed into a film, and the organic solvents such as the reaction solvent and the dilution solvent contained in the varnish can be removed by heating to obtain polyamide Acid film, and the polyimide in the polyimide film is imidized by heating to produce the polyimide film. The heating temperature when drying the polyamic acid varnish to obtain the polyamic acid film is preferably 50 to 120°C. The heating temperature when the polyamide acid is imidized by heating is preferably 200 to 400°C. In addition, the method of imidization is not limited to thermal imidization, and chemical imidization may also be used.

＜Copolymer varnish＞ In addition, the polyimide film can also be produced using a copolymer varnish obtained by dissolving the above-mentioned copolymer 3 in an organic solvent. The copolymer varnish is formed by dissolving the copolymer 3, which is the precursor of the polyimide resin, in an organic solvent. That is, the copolymer varnish contains the copolymer 3 and an organic solvent, and the copolymer 3 is dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the copolymer 3. As the solvent used in the manufacture of the copolymer 3, the above-mentioned compounds are preferably used alone or in combination of two or more. The copolymer varnish may be the above-mentioned copolymer solution itself, or may be obtained by further adding a diluting solvent to the copolymer solution.

Considering the viewpoint that the imidization of the amide acid part in the copolymer 3 can be carried out efficiently, the copolymer varnish may further contain an imidization catalyst and a dehydration catalyst. Regarding the imidization catalyst, any catalyst having a boiling point of 40° C. or higher and 180° C. or lower may be used, and an amine compound having a boiling point of 180° C. or lower is preferable. If it is an imidization catalyst with a boiling point below 180°C, there is no risk that the film will be colored after the film is formed and dried at high temperatures, which may impair the appearance. In addition, if it is an imidization catalyst with a boiling point of 40°C or higher, the possibility of volatilization before the imidization fully progresses can be avoided. As the amine compound ideally used as an imidization catalyst, pyridine or picoline can be cited. The above-mentioned imidization catalysts can be used alone or in combination of two or more kinds. Examples of the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These can be used individually or in combination of 2 or more types.

The copolymer 3 contained in the copolymer varnish has solvent solubility, so it can be made into a high-concentration varnish. The copolymer varnish preferably contains 5-40% by mass of copolymer 3, more preferably 10-30% by mass. The viscosity of the copolymer varnish is preferably 0.1-100Pa･s, and more preferably 0.1-20Pa･s. The viscosity of the copolymer varnish is a value measured at 25°C using an E-type viscometer. In addition, the copolymer varnish can also contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, and leveling agents within the range that does not impair the required characteristics of the polyimide film. , Defoamer, fluorescent whitening agent, crosslinking agent, polymerization initiator, sensitizer and other additives. The manufacturing method of the varnish is not specifically limited, A well-known method can be used.

The heating temperature when drying the copolymer varnish to obtain a copolymer film is preferably 50 to 150°C. The heating temperature when the copolymer 3 is imidized by heating can be selected from the range of 200-500°C, preferably 250-450°C, and still more preferably 300-400°C. In addition, the heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour. The heating environment can include air, nitrogen, oxygen, hydrogen, nitrogen/hydrogen mixed gas, etc., in order to suppress the coloration of the obtained polyimide resin, nitrogen with an oxygen concentration of 100ppm or less, and nitrogen/hydrogen with a hydrogen concentration of 0.5% or less Mixed gas is preferred. In addition, the method of imidization is not limited to thermal imidization, and chemical imidization may also be used.

[Adjustment of moisture content of polyimide film] The moisture content of the polyimide film in the present invention is 1,000 to 35,000 ppm by mass. The method of adjusting the moisture content of the polyimide film within this range is not particularly limited, and the polyimide varnish can be made to contain moisture when the polyimide varnish is coated on a glass substrate or a silicon substrate to produce the polyimide film. However, it is suitable to make the polyimide film better absorb moisture. In addition, after the polyimide film is produced, a metal film or an oxide semiconductor film is subsequently laminated on the film, and various electronic devices are manufactured to make them absorb moisture. In order to make the polyimide film absorb moisture, the temperature is preferably 10-40°C, more preferably 15-35°C, humidity is 40-80%RH, more preferably 50-70%RH, particularly preferably 55 Keep it for a predetermined time under a temperature and humidity environment of ~65%RH. The holding time will also be affected by temperature and humidity, but it is preferably 20 hours or more, more preferably 40 hours or more, still more preferably 60 hours or more, usually within 170 hours. In addition, RH means relative humidity.

(Metal film or oxide semiconductor film) In the laminated system of the present invention, a metal film or an oxide semiconductor film is further laminated on the polyimide film. By laminating a metal film or an oxide semiconductor film on the polyimide film, a touch sensor, OLED, etc. can be made on the polyimide film as a target electronic device (conductive film). Preferable specific examples of the metal film include copper mesh, silver mesh, and the like. Ideal specific examples of the oxide semiconductor film include at least one selected from the group consisting of indium tin oxide (ITO), amorphous silicon, indium-gallium-zinc oxide (IGZO), and low-temperature polysilicon (LTPS). Another metal film or oxide semiconductor film may be further laminated on these metal films or oxide semiconductor films. Considering the viewpoint of fabricating electronic devices on a polyimide film, the thickness of the metal film or oxide semiconductor film is 1 to 400 nm, preferably 10 to 300 nm, and more preferably 20 to 200 nm.

The method of laminating a metal film or an oxide semiconductor film on the polyimide film is not particularly limited, and it is preferably a physical vapor deposition method or a chemical vapor deposition method. Examples of physical vapor deposition methods include vacuum vapor deposition methods, sputtering methods, ion plating methods, and the like, and chemical vapor deposition methods include plasma chemical vapor deposition methods, thermochemical vapor deposition methods, and photochemical vapor deposition methods.

By peeling and removing the glass substrate or the silicon substrate from the laminate on which the metal film or the oxide semiconductor film is laminated, a conductive thin film can be obtained. That is, the manufacturing method of the conductive thin film of this invention includes the step of peeling and removing a glass substrate or a silicon substrate from the said laminated body. After making a conductive film by laminating a metal film or an oxide semiconductor film on a polyimide film, immediately peel off the glass substrate or silicon substrate to obtain a conductive film. It can also be stored in a laminate state, if necessary The glass substrate or the silicon substrate is peeled off to obtain a conductive thin film. If it is stored in the state of a laminated body, the operability during transportation of the conductive film is improved, which is preferable.

The method for peeling and removing the glass substrate or the silicon substrate from the laminate is not particularly limited. The laminate of the present invention can easily and stably peel the polyimide film from the glass substrate or the silicon substrate, so laser irradiation is not necessary. And mechanically peeled off. [Example]

Hereinafter, the present invention will be specifically explained using examples. However, the present invention is not limited to these embodiments.

In the examples and comparative examples, each physical property was measured by the method shown below. (1) Film thickness The film thickness was measured using a laser microscope (manufactured by Keyence Co., Ltd.).

(2) Glass transition temperature (Tg) Using the thermomechanical analyzer "TMA/SS6100" (manufactured by Hitachi High-Tech Science Co., Ltd.), the temperature is raised in a tensile mode under the conditions of a sample size of 2mm×20mm, a load of 0.1N, and a heating rate of 10°C/min. The temperature is sufficient to remove the residual stress to remove the residual stress, and then cool to room temperature. Then, the elongation of the test piece was measured under the same conditions as the above-mentioned treatment for removing the residual stress, and the temperature at which the inflection point of the elongation was observed was determined as the glass transition temperature.

(3) Total light transmittance, yellow index (YI) The total light transmittance and YI are measured in accordance with JIS K7105:1981 using a color-turbidity simultaneous measuring device "COH400" (manufactured by Nippon Denshoku Industries Co., Ltd.).

(4) Thickness phase difference (Rth) The thickness phase difference (Rth) was measured using an ellipsometer "M-220" (manufactured by JASCO Corporation). The value of the thickness retardation at the measurement wavelength of 590 nm is measured. In addition, in terms of Rth, when the largest in-plane refractive index of the polyimide film is nx, the smallest is ny, the refractive index in the thickness direction is nz, and the thickness of the film is d, it is expressed by the following formula. Rth=[{(nx＋ny)/2}-nz]×d

(5) Moisture content of polyimide film The film was measured at 260°C for 30 minutes by Karl Fischer method. As for the measuring equipment, the trace moisture measuring device "CA-200" (made by Mitsubishi Chemical Analytech Co., Ltd., the moisture meter of Karl Fischer method), and the moisture vaporization device "VA-236S" (Mitsubishi Chemical Analytech Co., Ltd.) are used. )Company system, with sample changer).

(6) Peel strength According to JIS K6854-1, a 90° peel test was carried out to measure the peel strength of the interface between the polyimide film and the glass. The peel strength was measured 5 times, and the average value was taken as the peel strength.

The tetracarboxylic acid component, diamine component, other components, and their abbreviations used in the production examples are as follows. ＜Tetracarboxylic acid component＞ HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.; compounds represented by formulas (a-11) and (a-21)) ODPA: 4,4'-oxydiphthalic anhydride (manufactured by MANAC Co., Ltd.; compounds represented by formulas (a-12) and (a-22)) CpODA: Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (JX Energy ( Stock) company system; compound represented by formula (a-31-1)) s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, a compound represented by formula (a-32-1s)) ＜Diamine component＞ 3,3'-DDS: 3,3'-diaminodiphenyl sulfide (manufactured by SEIKA Co., Ltd.; compounds represented by formulas (b-11) and (b-21)) BAPS: Bis[4-(4-aminophenoxy)phenyl] sulfide (manufactured by SEIKA Co., Ltd.; compound represented by formula (b-12)) HFBAPP: 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (manufactured by SEIKA Co., Ltd.; compound represented by formula (b-22-3)) 6FODA: 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (manufactured by ChinaTech (Tianjin) Chemical Co., Ltd., compound represented by formula (b-31)) X-22-1660B-3: Two-terminal amine modified polysiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (b-32) (functional group equivalent: 2200g/mol or 2170g/mol) ＜Other＞ GBL: γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) TEA: Triethylamine (manufactured by Kanto Chemical Co., Ltd.) NMP: N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation)

Manufacturing example 1 Put into a 300mL 5-neck round-bottomed flask equipped with a stainless steel half-moon stirring wing, nitrogen introduction tube, Dean-Stark equipped with a cooling tube, thermometer, and glass end cap, put 13.845g (0.056 mol) of 3, 3'-DDS, 24.115g (0.056 mol) of BAPS, and 41.903g of GBL were stirred at a system temperature of 70°C and a nitrogen environment at a rotation speed of 200 rpm to obtain a solution. In this solution, 22.499g (0.100 mol) of HPMDA, 3.459g (0.011 mol) of ODPA, and 12.804g of GBL were added all at once, and then 0.564g of TEA as an imidization catalyst was added. The heating mantle heated, which took about 20 minutes to raise the temperature in the reaction system to 190°C. The distilled components were collected, and the rotation speed was adjusted to increase the viscosity while maintaining the temperature in the reaction system at 190°C and refluxing for about 5 hours. Then, 175.981 g of GBL was added so that the solid content concentration might become 20 mass %, and after cooling the temperature in the reaction system to 100 degreeC, it stirred for about 1 hour, and homogenized, and obtained polyimide varnish 1. Then, the obtained polyimide varnish 1 was applied on a glass plate by spin coating, and kept at 80°C for 20 minutes on a hot plate, and then heated at 260°C for 30 minutes in a hot air dryer in an air environment to make The solvent evaporates to obtain a thin film.

Manufacturing example 2 Put into a 300mL 5-neck round-bottomed flask equipped with stainless steel half-moon stirring blades, nitrogen inlet pipe, Dean-Stark equipped with cooling pipe, thermometer, and glass end cap, and put 23.530g (0.094 mol) of 3, 3'-DDS, 12.247g (0.024 mol) of HFBAPP, and 62.820g of GBL were stirred at a system temperature of 70°C and a nitrogen environment at a rotation speed of 200 rpm to obtain a solution. In this solution, 21.158g (0.094 mol) of HPMDA, 7.313g (0.024 mol) of ODPA, and 15.705g of GBL were added all at once, and then 0.596g of TEA as an imidization catalyst was added, and used The heating mantle heated, which took about 20 minutes to raise the temperature in the reaction system to 190°C. The distilled components were collected, and the rotation speed was adjusted to increase the viscosity while maintaining the temperature in the reaction system at 190°C and refluxing for 5 hours. Then, 161.475 g of GBL was added so that the solid content concentration might become 20 mass %, and after cooling the temperature in the reaction system to 100 degreeC, it stirred for about 1 hour, and homogenized, and obtained the polyimide varnish 2. Then, the obtained polyimide varnish 2 was coated on a glass plate by spin coating, and kept at 80°C for 20 minutes on a hot plate, and then heated at 260°C for 30 minutes in a hot air dryer in an air environment to make The solvent evaporates to obtain a thin film.

Manufacturing example 3 Into a 500mL 5-neck round bottom flask equipped with stainless steel half-moon stirring blades, nitrogen introduction tube, Dean-Stark equipped with cooling tube, thermometer, and glass end cap, put 26.953g (0.0802 mol) of 6FODA, And 56.000 g of NMP, stirred at a rotation speed of 200 rpm under a system temperature of 70° C. under a nitrogen environment to obtain a solution. In this solution, add 19.231g (0.050 mol) of CpODA and 14.000g of NMP at one time, put in 0.253g of TEA as the imidization catalyst, and use a heating mantle to heat it for about 20 minutes to make the reaction The temperature in the system rose to 190°C. The distilled components were collected, and the rotation speed was adjusted to increase the viscosity while maintaining the temperature in the reaction system at 190°C and refluxing for 1 hour. After that, 85.806 g of NMP was added, and the temperature in the reaction system was cooled to 50° C. to obtain a solution containing an oligomer having an imine repeating structural unit. To the obtained solution, 9.814 g (0.033 mol) of s-BPDA and 7.527 g of NMP were added all at once, and stirred at 50°C for 5 hours. Then, after adding 100.000g of NMP and homogenizing it, put into 16.667g of NMP dissolved 14.002g (0.003 mol) of X-22-1660B-3 mixed liquid, and further stirred for about 1 hour to obtain a solid Varnish 3 containing copolymer (PI-b-PAA) with a component concentration of about 20% by mass. Here, the copolymer having the amide repeating structural unit and the amide repeating structural unit is referred to as "PI-b-PAA". Then, the obtained varnish 3 was coated on a glass plate by spin coating, and kept at 80°C for 20 minutes on a hot plate, and then heated at 350°C for 30 minutes in a hot air dryer in an air environment to evaporate the solvent. Polyimide film.

The above-mentioned measurement was performed on the polyimide films obtained in Production Examples 1 to 3. The results are shown in Tables 1 and 2.

[Table 1] PI Manufacturing example 1 Manufacturing example 2 Polyimide composition Tetracarboxylic acid composition (mol%) HPMDA 90 80 ODPA 10 20 Diamine component (mol%) 3,3'-DDS 50 80 BAPS 50 HFBAPP 20 Polyimide film evaluation membrane thickness μm 10 10 Tg °C 299 281 Total light transmittance % 89.8 90.01 YI 0.31 1.27 Rth nm 26 32

[Table 2] Manufacturing example 3 Copolymer composition Tetracarboxylic acid component (mol%) CpODA 60 s-BPDA 40 Diamine component (mol%) 6FODA 96.13 X-22-1660B-3 3.87 Polyorganosiloxane unit content (mass%) 20 The structure of the copolymer PI-b-PAA Film evaluation membrane thickness μm 10 Tg °C 324 Total light transmittance % 91.58 YI 2.24 Rth nm 79.7

Examples 1 to 2 and Comparative Example 1 The polyimide varnish 1 obtained in Production Example 1 was coated on a glass plate by spin coating, and kept at 80°C for 20 minutes on a hot plate. It heated at 260°C for 30 minutes in a dryer to evaporate the solvent to obtain a two-layer laminate (glass/polyimide film). _{Furthermore, a SiO 2} film with a thickness of 30 nm was formed by sputtering on the polyimide film of the laminate, and an ITO film with a thickness of 120 nm was formed thereon to obtain a 4-layer laminate (glass/polyimide film/SiO ₂ film/ITO film). The obtained 4-layer laminate was maintained under the conditions described in Table 3, and the moisture content of the polyimide film in the 4-layer laminate was adjusted.

Examples 3 to 4 and Comparative Example 2 The polyimide varnish 2 obtained in Production Example 2 was coated on a glass plate by spin coating, and kept at 80°C for 20 minutes on a hot plate. It heated at 260°C for 30 minutes in a dryer to evaporate the solvent to obtain a two-layer laminate (glass/polyimide film). _{Furthermore, a SiO 2} film with a thickness of 30 nm was formed by sputtering on the polyimide film of the laminate, and an ITO film with a thickness of 120 nm was formed thereon to obtain a 4-layer laminate (glass/polyimide film/SiO ₂ film/ITO film). The obtained 4-layer laminate was maintained under the conditions described in Table 3, and the moisture content of the polyimide film in the 4-layer laminate was adjusted.

Examples 5 to 6 The varnish 3 obtained in Manufacturing Example 3 was coated on a glass plate by spin coating, and kept at 80°C for 20 minutes on a hot plate, and then heated at 350°C in a hot air dryer in an air environment for 30 minutes. In minutes, the solvent was evaporated to obtain a two-layer laminate (glass/polyimide film). _{Furthermore, a SiO 2} film with a thickness of 30 nm was formed by sputtering on the polyimide film of the laminate, and an ITO film with a thickness of 120 nm was formed thereon to obtain a 4-layer laminate (glass/polyimide film/SiO ₂ film/ITO film). The obtained 4-layer laminate was maintained under the conditions described in Table 3, and the moisture content of the polyimide film in the 4-layer laminate was adjusted.

The above-mentioned peeling test was performed on the laminate obtained above. The results are shown in Table 3. In addition, the laminate of Comparative Example 1 could not peel the film from the glass, and could not measure the peel strength. In addition, the laminate of Comparative Example 2 was broken when the film was peeled from the glass, and the peel strength could not be measured.

[table 3] Example 1 Example 2 Comparative example 1 Example 3 Example 4 Comparative example 2 Example 5 Example 6 Types of polyimide Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Polyimide film thickness μm 10 5 7 Moisture content of polyimide film Mass ppm 8000 5000 0 3000 1000 300 6000 12000 Keep condition °C twenty three twenty three - 18 18 twenty three 25 25 %RH 50 65 - 70 55 20 45 75 hr 168 80 0 50 twenty four 1 120 150 Peel strength gf/cm 3.4 5.4 Can't peel off 9 18 fracture 5.2 4.1

From the results in Table 3, it can be seen that the laminate of the present invention in which the moisture content of the polyimide film is adjusted within a predetermined range has relatively low peel strength, and the polyimide film can be easily and stably removed from the glass substrate. Or the silicon substrate is peeled off. In addition, it can be seen from the results of Tables 1 and 2 that the polyimide films of Production Examples 1 to 3 are excellent in colorless transparency and optical isotropy.

Claims (8)

A laminated body is formed by closely adhering a polyimide film on a glass substrate or a silicon substrate, and further laminating a metal film or an oxide semiconductor film on the polyimide film; The thickness of the metal film or the oxide semiconductor film is 1 to 400 nm, and the moisture content of the polyimide film is 1,000 to 35,000 mass ppm. The laminate of claim 1, wherein the peel strength of the polyimide film when peeled from the glass substrate or the silicon substrate is 20 gf/cm or less. The laminate of claim 1 or 2, wherein the polyimide film has a film thickness of 3-20 μm. The laminate of any one of claims 1 to 3, wherein the oxide semiconductor film is selected from at least the group consisting of indium tin oxide, amorphous silicon, indium-gallium-zinc oxide and low-temperature polysilicon One. A conductive film obtained by peeling and removing the glass substrate or the silicon substrate from the laminated body of any one of claims 1 to 4. A method for manufacturing a conductive film includes the following steps: Laminating polyimide film on glass substrate or silicon substrate; Adjust the moisture content of the polyimide film to 1,000-35,000 ppm by mass; Laminating a metal film or oxide semiconductor film with a thickness of 1 to 400 nm on the polyimide film; and Peel off the glass substrate or silicon substrate. The method of manufacturing a conductive film according to claim 6, wherein the step of adjusting the moisture content of the polyimide film is to maintain the polyimide film at a temperature and humidity of 10-40°C and 40-80%RH More than 20 hours in the environment. According to claim 6 or 7, the method of manufacturing a conductive thin film, wherein the step of laminating a metal film or an oxide semiconductor film on the polyimide thin film adopts a physical vapor deposition method or a chemical vapor deposition method.