TW202224947A - Polyimide film and production method therefor - Google Patents

Abstract

Provided are a colorless polyimide film which is high in tensile rupture strength and tensile modulus and has a high elongation at rupture and a low coefficient of linear expansion and a method for producing the polyimide film. The polyimide film is a multilayered polyimide film having a thickness of 3-120 [mu]m, a yellowness index of 5 or less, and a total light transmittance of 86% or greater, characterized by having a multilayer structure in which at least two polyimide layers differing in composition have been superposed in the thickness direction and in that the two polyimide layers include an (a) layer and a (b) layer, the (a) layer having a film thickness of 0.3 [mu]m or larger and the (b) layer having a film thickness 5-25 times that of the (a) layer.

Description

Polyimide film and method for producing the same

The present invention relates to a colorless polyimide film with low coefficient of linear expansion and good mechanical properties and a manufacturing method thereof.

Polyimide films are widely used in electrical and electronic fields as materials having excellent heat resistance, good mechanical properties, and flexibility. However, since a normal polyimide film is colored yellowish-brown, it cannot be applied to a portion that needs to transmit light, such as a display device. On the other hand, display devices are being made thinner and lighter, and further flexibility is being pursued. Therefore, an attempt was made to replace the substrate material from a glass substrate to a flexible polymer film substrate, but the colored polyimide film could not be used as a substrate material for a liquid crystal display that performs display by transmitting light through ON/OFF. It can only be applied to peripheral circuits such as TAB and COF mounted with the drive circuit of the display device, and to very few parts such as the rear side of the reflective display method or self-luminous display device.

From this background, the development of a colorless and transparent polyimide film was carried out. As a representative example, attempts have been made to develop colorless and transparent polyimide films using fluorinated polyimide resins, semi-alicyclic or fully alicyclic polyimide resins (Patent Documents 1 to 3). These films are less colored and have transparency, but their mechanical properties cannot be improved to the level of colored polyimide films. When industrial production is assumed, and applications exposed to high temperatures are used, thermal decomposition or oxidation reactions will occur. Colorless and transparent are not necessarily maintained. From this point of view, a method of heat treatment while spraying a gas with a predetermined oxygen content has been proposed (Patent Document 4). However, in an environment where the oxygen concentration is less than 18%, the manufacturing cost is high and industrial production is extremely difficult. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-106508 [Patent Document 2] Japanese Patent Laid-Open No. 2002-146021 [Patent Document 3] Japanese Patent Laid-Open No. 2002-348374 [Patent Document 4] WO2008/146637

[The problem to be solved by the invention]

Half-alicyclic or fully alicyclic polyimide, if the monomer component having an alicyclic structure is added, although colorless transparency is obtained, it becomes hard and brittle, the elongation at break decreases, and production as a film becomes difficult. . On the other hand, when an aromatic monomer or a monomer having an amide bond in the molecule is introduced, the toughness is improved and the mechanical properties of the film are improved, but it becomes easy to be colored and the colorless transparency is lowered. By introducing an inorganic component with a refractive index close to that of the resin component, heat resistance and colorless transparency are improved, the coefficient of linear expansion is further reduced, and processing suitability is improved, but the resin becomes hard and brittle in terms of physical properties, and mechanical properties are reduced. That is, it is very difficult to manufacture a transparent polyimide film that satisfies all colorless properties because of a trade-off between practical properties such as heat resistance and mechanical properties and colorless transparency. [means to solve the problem]

The present inventors attempted to realize a balanced polyimide film by combining a plurality of polyimide resins. Usually, when resins of multiple components are combined and blended, mixed, or copolymerized, it is not always possible to obtain a result that only combines the advantages of each component, but there are many examples where the disadvantages are multiplied and manifested. However, the inventors of the present invention have continued to study hard, and as a result, they have found that the present invention can be achieved by combining the polyimide resins so as to form a specific structure and forming a thin film so that the advantages of each component can be fully utilized. That is, the present invention has the following configuration. [1] A multilayer polyimide film comprising at least a polyimide layer (a) and a polyimide layer (b), wherein The polyimide layer (a) and the polyimide layer (b) are different in composition, The film thickness of the polyimide layer (a) is 0.3 μm or more, The film thickness of the polyimide layer (b) is 5 times or more and 25 times or less the film thickness of the polyimide layer (a) layer, The multilayer polyimide film has a thickness of 3 μm or more and 120 μm or less, a yellowness index of 5 or less, and a total light transmittance of 86% or more. [2] The multilayer polyimide film according to [1], wherein the layers (a) and (b) are mainly composed of polyimide having the following characteristics; Layer (a): Polyimide with a yellow index of 10 or less and a total light transmittance of 85% or more when it is individually made into a film with a thickness of 25±2 μm (b) Layer: Polyimide having a yellow index of 5 or less and a total light transmittance of 90% or more when it is individually formed into a thin film with a thickness of 25±2 μm. [3] The multi-layer polyimide film according to [1] or [2], wherein the polyimide in the layer (a) is a polymer having a chemical structure obtained by polycondensation of tetracarboxylic anhydride and diamine imide, The aforementioned tetracarboxylic anhydrides contain at least one selected from the group consisting of alicyclic tetracarboxylic anhydrides, aromatic tetracarboxylic anhydrides having ether groups in the molecule, and aromatic tetracarboxylic anhydrides having biphenyl groups in the molecule tetracarboxylic anhydride, The said diamine contains 1 or more types of diamines chosen from the group which consists of the diamine which has an amide bond in a molecule|numerator, and the diamine which has a trifluoromethyl group in a molecule|numerator. [4] The multilayer polyimide film according to any one of [1] to [3], wherein the polyimide of the (b) layer comprises a polyimide obtained by polycondensation of tetracarboxylic anhydride and diamine Chemically constructed polyimide, The aforementioned tetracarboxylic anhydrides are selected from the group consisting of alicyclic tetracarboxylic anhydrides, aromatic tetracarboxylic anhydrides having ether groups in the molecule, aromatic tetracarboxylic anhydrides having biphenyl groups in the molecule, and trifluorocarbons in the molecule. One or more tetracarboxylic anhydrides of the group of methyl aromatic tetracarboxylic anhydrides, The said diamine contains 1 or more types of diamine chosen from the group which consists of a diamine which has a sulfo group in a molecule|numerator, and a diamine which has a trifluoromethyl group in a molecule|numerator. [5] A method for producing a multilayer polyimide film as described in any one of [1] to [4], comprising at least: 1: the step of coating (a) the polyimide solution or polyimide precursor solution for layer formation on the temporary support to obtain the coating film a1; 2: within 100 seconds after the coating film a1 is made, the polyimide solution or the polyimide precursor solution for layer formation (b) is applied to the coating film a1 to obtain the coating film ab1 The step of; 3: the step of heating the coating film ab1 to obtain the coating film ab2 with a residual solvent content of 15-40 mass % on the basis of the whole coating film; 4: the step of peeling off the coating film ab2 from the temporary support; 5: heating the coating film ab2 at a temperature of 150°C or more and less than 200°C to obtain a coating film ab3 with a residual solvent content of 5% by mass or more and less than 15% by mass on the basis of the whole coating film; 6: A step of heating the coating film ab3 to obtain the coating film ab4 having a residual solvent content of 0.5 mass % or less on the basis of the entire coating film. [Effect of invention]

The present invention achieves excellent optical properties (colorless transparency) without inconveniences such as warpage by constituting a film with a plurality of layers including different compositions, and further has the advantage of being able to obtain sufficient handleability as a flexible film. Heat resistant film with mechanical properties.

The chemical structure of the polyimide of the layer (a) in the present invention is not limited, but it is preferably a polyimide having a chemical structure obtained by polycondensation of the following tetracarboxylic anhydride and the following diamine: One or more tetracarboxylic anhydrides selected from the group consisting of alicyclic tetracarboxylic anhydrides, aromatic tetracarboxylic anhydrides having an ether group in the molecule, and aromatic tetracarboxylic anhydrides having biphenyl groups in the molecule; and containing One or more kinds of diamines selected from the group consisting of diamines having an amide bond in the molecule and diamines having a trifluoromethyl group in the molecule. The total amount of the alicyclic tetracarboxylic anhydride, the aromatic tetracarboxylic acid having an ether group in the molecule, and the aromatic tetracarboxylic anhydride having a biphenyl group in the molecule is 70 mol% or more in the tetracarboxylic anhydride More preferably, it is 80 mol % or more, more preferably 90 mol % or more, particularly preferably 95 mol % or more, and 100 mol %. Moreover, the total amount of the diamine having an amide bond in the molecule and the diamine having a trifluoromethyl group in the molecule is preferably 70 mol % or more, more preferably 80 mol % in the aforementioned diamines. Above, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and 100 mol%. By setting it in the said range, the mechanical property of a multilayer polyimide film becomes favorable. The chemical structure of the polyimide of the other (b) layer is not limited, but is preferably a polyimide having a chemical structure obtained by polycondensation of the following tetracarboxylic anhydride and the following diamine: Contains alicyclic tetracarboxylic anhydrides, aromatic tetracarboxylic anhydrides having ether groups in the molecule, aromatic tetracarboxylic anhydrides having biphenyl groups in the molecule, and aromatic tetracarboxylic anhydrides having a trifluoromethyl group in the molecule One or more tetracarboxylic anhydrides of the group of ; containing one or more diamines selected from the group consisting of diamines having a sulfo group in the molecule and diamines having a trifluoromethyl group in the molecule. The aforementioned alicyclic tetracarboxylic anhydrides, aromatic tetracarboxylic anhydrides having an ether group in the molecule, aromatic tetracarboxylic anhydrides having a biphenyl group in the molecule, and aromatic tetracarboxylic anhydrides having a trifluoromethyl group in the molecule The total amount is preferably more than 70 mol % in the aforementioned tetracarboxylic anhydride, more preferably more than 80 mol %, further preferably more than 90 mol %, particularly preferably more than 95 mol %, and 100 mol % or more. % is fine. Moreover, the total amount of the diamine having a sulfo group in the molecule and the diamine having a trifluoromethyl group in the molecule is preferably 70 mol % or more, more preferably 80 mol %, in the diamine component. Above, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and 100 mol%. By setting it in the said range, the transparency of a multilayer polyimide film becomes favorable. When the two are mixed or copolymerized, only a film with physical properties in between or less than the two can be obtained, and the colorless transparency tends to be influenced by the properties of the (a) layer which is easy to color.

However, as in the present invention, by forming these two kinds of polyimides as independent layers to share functions, and further applying a specific production method, a balance can be achieved, that is, colorless transparency and A film with practically sufficient film strength, high elongation at break, and low coefficient of linear expansion. The polyimide film is obtained by coating the polyimide solution or the polyimide precursor solution on the support, drying it, and performing chemical reactions as needed. A production method of coating with a short time difference (preferably at the same time) is characteristic. That is, by applying the resin constituting the layer (a) and the resin constituting the layer (b), which are two different components, respectively, to have a limited thickness, the residual solvent amount at the time of drying is further limited. range, the dry state of layer (a) can be distinguished from the dry state of layer (b). As a result, the warpage due to the difference in CTE between the (a) layer and the (b) layer is reduced, and a well-balanced thin film can be obtained without the internal strain being concentrated in a specific portion.

[Form for carrying out the invention]

The multilayer polyimide film of the present invention has a thickness of 3 μm or more and 120 μm or less. From the viewpoint of improving mechanical properties, the thickness is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 8 μm or more. Moreover, 100 micrometers or less is preferable in terms of transparency becoming favorable, 80 micrometers or less are more preferable, and 60 micrometers or less are still more preferable.

The multi-layer polyimide film of the present invention has a yellowness index of 5 or less. From the viewpoint of improving transparency, it is preferably 4 or less, more preferably 3.5 or less, and still more preferably 3 or less. The lower limit is not particularly limited because the yellowness index is preferably lower, but industrially, it may be 0.1 or more, or 0.2 or more.

The total light transmittance of the multilayer polyimide film of the present invention is above 86%. From the viewpoint of improving transparency, it is preferably 87% or more, more preferably 88% or more, and still more preferably 89% or more. The upper limit is not particularly limited, but industrially, it may be 99% or less, or 98% or less.

In the present invention, two types of polyimides having different compositions are used, and these are stacked in the thickness direction. Polyimide is usually a polymer obtained by the polycondensation reaction of tetracarboxylic anhydride and diamine. It is preferable that the said two types of polyimide layers comprise (a) layer and (b) layer, and said (a) layer and (b) layer are respectively comprised mainly by the polyimide of the following characteristics. Here, "mainly" means that the polyimide having the following properties is preferably contained in each layer in an amount of 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

Polyimide mainly used in layer (a) (hereinafter, "main" is sometimes omitted, and only described as "polyimide used in layer (a)" or "polyimide used as layer (a)" " etc. ) is preferably a polyimide with a yellow index of 10 or less and a total light transmittance of 85% or more when it is individually made into a film with a thickness of 25±2 μm. From the viewpoint of improving transparency, the yellowness index is preferably 9 or less, more preferably 8 or less, and still more preferably 7 or less. The lower limit of the yellowness index is not particularly limited, but industrially, it may be 0.1 or more, and 0.2 or more may be acceptable. The total light transmittance is preferably 86% or more, more preferably 87% or more, and further preferably 88% or more. The upper limit is not particularly limited, but industrially, it may be 99% or less, or 98% or less.

The thickness (film thickness) of the (a) layer in the multilayer polyimide film is 0.3 μm or more. From the viewpoint of improving the mechanical strength, it is preferably greater than 0.3 μm, more preferably 0.4 μm or more, and even more preferably 0.5 μm or more. Furthermore, from the viewpoint of improving transparency, 20 μm or less is preferable, 10 μm or less is more preferable, 7.5 μm or less is further preferable, and 5 μm or less is particularly preferable.

The chemical structure of the polyimide mainly used for the layer (a) is not limited, but it is preferably a polyimide containing a chemical structure obtained by polycondensation of tetracarboxylic anhydride and diamine. The tetracarboxylic anhydride preferably contains one selected from the group consisting of an alicyclic tetracarboxylic anhydride, an aromatic tetracarboxylic anhydride having an ether group in the molecule, and an aromatic tetracarboxylic anhydride having a biphenyl group in the molecule more than one tetracarboxylic anhydride. Moreover, it is preferable that the said diamine contains 1 or more types of diamines chosen from the group which consists of a diamine which has an amide bond in a molecule|numerator, and a diamine which has a trifluoromethyl group in a molecule|numerator. The total amount of the alicyclic tetracarboxylic anhydride, the aromatic tetracarboxylic acid having an ether group in the molecule, and the aromatic tetracarboxylic anhydride having a biphenyl group in the molecule is 70 mol% or more in the tetracarboxylic anhydride More preferably, it is 80 mol % or more, more preferably 90 mol % or more, particularly preferably 95 mol % or more, and 100 mol %. Moreover, the total amount of the diamine having an amide bond in the molecule and the diamine having a trifluoromethyl group in the molecule is preferably 70 mol % or more, more preferably 80 mol % in the aforementioned diamines. Above, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and 100 mol%. By setting it in the said range, the mechanical property of a multilayer polyimide film becomes favorable.

Polyimide mainly used in layer (b) (hereinafter, "main" is sometimes omitted, and only described as "polyimide used in layer (b)" or "polyimide used in layer (b)" " etc. ) is preferably a polyimide with a yellow index of 5 or less and a total light transmittance of 90% or more when it is individually made into a film with a thickness of 25±2 μm. From the viewpoint of improving transparency, the yellowness index is preferably 4 or less, more preferably 3 or less. The lower limit of the yellowness index is not particularly limited, but industrially, it may be 0.1 or more, and 0.2 or more may be acceptable. The total light transmittance is preferably 91% or more, more preferably 92% or more. The upper limit is not particularly limited, but industrially, it may be 99% or less, or 98% or less.

The thickness (film thickness) of the (b) layer in the multilayer polyimide film is 5 times or more and 25 times or less the film thickness of the above-mentioned (a) layer. From the viewpoint of improving transparency, it is preferably 7.5 times or more, and more preferably 10 times or more. Moreover, from the viewpoint of improving the mechanical strength, 23.5 times or less is preferable, and 20 times or less is more preferable.

From the viewpoint of improving the mechanical strength, the thickness of the (b) layer in the multilayer polyimide film is preferably 1.5 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and still more preferably 5 μm or more, particularly preferably 6 μm or more. Furthermore, from the viewpoint of improving transparency, it is preferably 115 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, and particularly preferably 50 μm or less.

The chemical structure of the polyimide mainly used in the (b) layer is not limited, but it is preferably a polyimide containing a chemical structure obtained by polycondensation of tetracarboxylic anhydride and diamine. The aforementioned tetracarboxylic anhydride preferably contains an alicyclic tetracarboxylic anhydride, an aromatic tetracarboxylic anhydride having an ether group in the molecule, an aromatic tetracarboxylic anhydride having a biphenyl group in the molecule, and an aromatic tetracarboxylic anhydride having a biphenyl group in the molecule. One or more tetracarboxylic anhydrides in the group of trifluoromethyl aromatic tetracarboxylic anhydrides. It is preferable that the said diamine contains 1 or more types of diamine chosen from the group which consists of a diamine which has a sulfo group in a molecule|numerator, and a diamine which has a trifluoromethyl group in a molecule|numerator. The aforementioned alicyclic tetracarboxylic anhydrides, aromatic tetracarboxylic anhydrides having an ether group in the molecule, aromatic tetracarboxylic anhydrides having a biphenyl group in the molecule, and aromatic tetracarboxylic anhydrides having a trifluoromethyl group in the molecule The total amount is preferably more than 70 mol % in the aforementioned tetracarboxylic anhydride, more preferably more than 80 mol %, further preferably more than 90 mol %, particularly preferably more than 95 mol %, and 100 mol % or more. % is fine. Moreover, the total amount of the diamine having a sulfo group in the molecule and the diamine having a trifluoromethyl group in the molecule is preferably 70 mol % or more, more preferably 80 mol %, in the diamine component. Above, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and 100 mol%. By setting it in the said range, the transparency of a multilayer polyimide film becomes favorable.

As the alicyclic tetracarboxylic anhydride in the present invention, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4 -cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3',4,4'-bicyclohexanetetracarboxylic acid, bicyclo[2,2,1]heptane-2 ,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3, 5,6-Tetracarboxylic acid, Tetrahydroanthracene-2,3,6,7-tetracarboxylic acid, Tetrahydro-1,4:5,8:9,10-Trimethylanthracene-2,3,6,7- Tetracarboxylic acid, decahydronaphthalene-2,3,6,7-tetracarboxylic acid, decahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid, decahydro-1, 4-Ethyl-5,8-methylnaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane -5,5'',6,6''-tetracarboxylic acid (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5' ',6,6''-tetracarboxylic acid"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)-5,5' ',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''- Tetracarboxylic acid (alias "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid"), Methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic acid, norbornate Alkane-2-spiro-α-cycloacetone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-ring Butanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cycloheptanone-α'-spiro- 2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane- 5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclononanone-α'-spiro-2''-norbornane-5,5'',6, 6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-5,5'',6,6''-tetracarboxylic acid Bornane-2-spiro-α-cycloundecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro- α-Cyclododecone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclotridecone- α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclotetradecone-α'-spiro-2' '-norbornane-5,5' ',6,6''-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2''-norbornane-5,5'',6,6'' -Tetracarboxylic acid, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, Norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid and other tetracarboxylic acids and such anhydrides. Among them, dianhydrides with two acid anhydride structures are preferred, especially 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclohexanetetracarboxylic dianhydride , 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride is further preferred. In addition, these may be used individually or in combination of 2 or more types.

In the present invention, the aromatic tetracarboxylic anhydride having an ether group in the molecule, the aromatic tetracarboxylic anhydride having a biphenyl group in the molecule, and the aromatic tetracarboxylic anhydride having a trifluoromethyl group in the molecule are respectively represented by Tetracarboxylic dianhydride is preferred. Specifically, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid, 4,4'-oxydiphthalic acid, bis(1,3-diphthalic acid) Oxy-1,3-dihydro-2-benzofuran-5-carboxylic acid) 1,4-phenylene, bis(1,3-dioxy-1,3-dihydro-2-benzofuran-5 -yl)benzene-1,4-dicarboxylate, 4,4'-[4,4'-(3-oxy-1,3-dihydro-2-benzofuran-1,1-diyl ) bis(benzene-1,4-diyloxy)]diphenyl-1,2-dicarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 4,4'-[(3 - Oxygen-1,3-dihydro-2-benzofuran-1,1-diyl)bis(toluene-2,5-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4, 4'-[(3-Oxygen-1,3-dihydro-2-benzofuran-1,1-diyl)bis(1,4-xylene-2,5-diyloxy)]di Benzene-1,2-dicarboxylic acid, 4,4'-[4,4'-(3-oxy-1,3-dihydro-2-benzofuran-1,1-diyl)bis(4- Isopropyl-toluene-2,5-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3-oxy-1,3-dihydro- 2-benzofuran-1,1-diyl)bis(naphthalene-1,4-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H -2,1-benzoxathiole-1,1-dioxide-3,3-diyl)bis(benzene-1,4-diyloxy)]diphenyl-1,2- Dicarboxylic acid, 4,4'-benzophenone tetracarboxylic acid, 4,4'-[(3H-2,1-benzooxythiol-1,1-dioxide-3,3-diyl)bis (Toluene-2,5-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[(3H-2,1-benzooxythiol-1,1-dioxide- 3,3-Diyl)bis(1,4-xylene-2,5-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H- 2,1-Benzothiol-1,1-dioxide-3,3-diyl)bis(4-isopropyl-toluene-2,5-diyloxy)]diphenyl-1, 2-Dicarboxylic acid, 4,4'-[4,4'-(3H-2,1-benzooxythiol-1,1-dioxide-3,3-diyl)bis(naphthalene-1, 4-Diyloxy)]diphenyl-1,2-dicarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-benzophenone tetra Formic acid, 3,3',4,4'-diphenyltetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, benzene Tetraacid, 4,4'-[spiro(dibenzopyran-9,9'-pyrene)-2,6-diylbis(oxycarbonyl)]diphthalic acid, 4,4'-[ Spiro(dibenzopyran-9,9'-pyrene)-3,6-diylbis(oxycarbonyl)]diphthalic acid and other tetracarboxylic acids and These acid anhydrides (acid dianhydrides). In addition, these aromatic tetracarboxylic acids may be used alone or in combination of two or more.

In the present invention, tricarboxylic acid and dicarboxylic acid can be used in addition to tetracarboxylic anhydride. As tricarboxylic acids, trimellitic acid, 1,2,5-naphthalene tricarboxylic acid, diphenyl ether-3,3',4'-tricarboxylic acid, diphenylene-3,3',4'- Aromatic tricarboxylic acids such as tricarboxylic acid, or hydrogenated products of the above aromatic tricarboxylic acids such as hexahydrotrimellitic acid, ethylene glycol bis-trimellitate, propylene glycol bis-trimellitate, 1,4-butane Alkanediol bis-trimellitate such as glycol bis-trimellitate and polyethylene glycol bis-trimellitate, and monoanhydrides and esters thereof. Among these, monoanhydrides having one acid anhydride structure are preferred, and trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferred. In addition, these may be used individually or in combination of two or more.

Examples of the dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and 4,4'-oxydibenzoic acid, or 1,6-ring Hydrogenates of the above aromatic dicarboxylic acids such as hexanedicarboxylic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, Dodecanedioic acid, 2-methylsuccinic acid, and acyl chlorides or esters of these. Among these, aromatic dicarboxylic acids and their hydrides are preferred, and terephthalic acid, 1,6-cyclohexanedicarboxylic acid, and 4,4'-oxydibenzoic acid are particularly preferred. In addition, the dicarboxylic acids may be used alone or in combination of two or more.

As a diamine which has an amide bond in a molecule|numerator in this invention, an aromatic diamine and an alicyclic amine can be mainly used. Examples of aromatic diamines include 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,4-bis[2-(4-aminophenyl)-2- Propyl]benzene, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy) ) phenyl] ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]thiane, 2,2-bis[4 -(3-Aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoro Propane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4-amino-N-(4-aminophenyl)benzylamide, 3, 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-trifluoromethyl-4,4'-diphenyl ether Amino diphenyl ether, 3,3'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfide, 3, 3'-diaminodiphenylene, 3,4'-diaminodiphenylene, 4,4'-diaminodiphenylene, 3,3'-diaminodiphenyl Diphenyl, 3,4'-diaminodiphenylene, 4,4'-diaminodiphenylene, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenylmethane Ketone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Phenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis [4-(4-Aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-bis[4-(4 -Aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) ) phenyl] propane, 1,1-bis[4-(4-aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane Alkane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2, 3-Bis[4-(4-aminophenoxy)phenyl]butane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminobenzene oxy)-3-methylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy) Phenoxy)phenyl]-2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy) base)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) Benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)benzene base] ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfene, bis[4-(4-amine bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3- Bis[4-(4-aminophenoxy)benzyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4- (3-Aminophenoxy)benzyl]benzene, 4,4'-bis[(3-aminophenoxy)benzyl]benzene, 1,1-bis[4-(3-amino]benzene Phenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3-(3-Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-Bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4- (3-Aminophenoxy)phenyl]sulfenylene, 4,4'-bis[3-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[3- (3-Aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone , 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylene, bis[4-{4-(4-aminophenoxy) Phenoxy}phenyl] benzene, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4- (4-Aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)- α,α-Dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3- Bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanobenzene oxy)-α,α-dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5, 5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxydi Benzophenone, 4,4'-Diamino-5-phenoxybenzophenone, 3,4'-Diamino-4-phenoxybenzophenone, 3,4'-Diamino -5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibenzoxybenzophenone, 4,4'-diamino- 5,5'-dibenzoxybenzophenone, 3,4'-diamino-4,5'-dibenzoxybenzophenone, 3,3'-diamino-4- Biphenoxybenzophenone, 4,4'-Diamino-5-biphenoxybenzophenone, 3,4'-Diamino-4-biphenoxybenzophenone, 3 ,4'-Diamino-5'-biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzyl)benzene, 1,4-bis(3- Amino-4-phenoxybenzyl)benzene, 1,3-bis(4-amino-5-phenoxybenzyl)benzene, 1,4-bis(4-amino-5-benzene) Oxybenzyl)benzene, 1,3-bis(3-amino-4-biphenoxybenzyl)benzene, 1,4-bis(3-amino-4-biphenoxybenzyl)benzene benzene, 1,3-bis(4-amino-5-biphenoxybenzyl)benzene, 1,4-bis(4-amino-5-biphenoxybenzyl)benzene, 2,6-Bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, 4,4'-[9H-perylene-9,9-diyl]dianiline (alias "9,9-bis(4-aminophenyl) fluoride"), spiro(dibenzopyran-9,9'- fluoride)-2,6-diylbis(oxycarbonyl)]bis Aniline, 4,4'-[spiro(dibenzopyran-9,9'-pyrene)-2,6-diylbis(oxycarbonyl)]dianiline, 4,4'-[spiro(diphenyl) Pyran-9,9'-Pyridine)-3,6-diylbis(oxycarbonyl)]dianiline, 5-amino-2-(p-aminophenyl)benzoxazole, 6-amine Base-2-(p-aminophenyl)benzoxazole, 5-amino-2-(m-aminophenyl)benzoxazole, 6-amino-2-(m-aminophenyl)benzene Acetazole, 2,2'-p-phenylene bis(5-aminobenzoxazole), 2,2'-p-phenylene bis(6-aminobenzoxazole), 1-(5 -aminobenzoxazolo)-4-(6-aminobenzoxazolo)benzene, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d : 5,4-d']bis oxazole, 2,6-(4,4'-diaminodiphenyl) benzo[1,2-d: 4,5-d'] bis oxazole, 2 ,6-(3,4'-Diaminodiphenyl)benzo[1,2-d:5,4-d']bisoxazole, 2,6-(3,4'-diaminodiphenyl) Phenyl)benzo[1,2-d:4,5-d']bisoxazole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:5 ,4-d'] two oxazoles, 2,6-(3,3'-diaminodiphenyl) benzo[1,2-d:4,5-d'] two oxazoles, etc. In addition, a part or all of the hydrogen atoms on the aromatic ring of the above-mentioned aromatic diamine may be substituted with a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or a cyano group, and the aforementioned alkyl group having 1 to 3 carbon atoms may be substituted. Alternatively, some or all of the hydrogen atoms of the alkoxy group may be further substituted with a halogen atom.

Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethyl cyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-propylcyclohexane Butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-secondarybutylcyclohexane, 1,4-diamino-2 -Tertiary butylcyclohexane, 4,4'-methylenebis(2,6-dimethylcyclohexylamine), 9,10-bis(4-aminophenyl)adenine, 2,4 - Dimethyl bis(4-aminophenyl)cyclobutane-1,3-dicarboxylate, etc.

In the present invention, it is preferable that the (a) layer of polyimide and the (b) layer of polyimide are two or more layers of (a)/(b), and the (b) layer is located on the upper layer (that is, in contact with the air). The surface (air surface)) is arranged. The linear expansion coefficient of the entire film can be kept low by making the (a) layer the lower layer (ie, the surface in contact with the coated support), which is superior in mechanical properties and has a small linear expansion coefficient compared to the (b) layer. On the other hand, the handleability of the film is improved, and the excellent optical properties of the upper layer (b) polyimide can be maximized. The layer (b) is preferably thicker than the layer (a). The ratio of the thickness (film thickness) of the (b) layer to the thickness (film thickness) of the (a) layer is (b) layer/(a) layer=5 or more, preferably 7.5 or more, and more preferably 10 or more. Again, it is 25 or less, preferably 23 or less, and more preferably 20 or less. In addition, the multilayer polyimide film of the present invention may have a multilayer structure of three or more layers. For example, a 3-layer configuration of (a) layer/(b) layer/(a) layer, a 4-layer configuration of (a) layer/(b) layer/(a) layer/(b) layer, (a) Layer/(b) layer/(a) layer/(b) layer/(a) layer composed of 5 layers. Furthermore, the multilayer polyimide film of the present invention may be laminated with layers other than the aforementioned (a) and (b) layers. Furthermore, the 3rd resin layer (c), the 4th resin layer (d) layer, etc. may be inserted in arbitrary layers in the range which does not impair the effect of this invention. In addition, depending on the use in a single-sided production device, etc., the roles pursued for the two sides of the corresponding film are different, so the composition or surface roughness of the two sides can be changed.

In the present invention, the thickness of the layer (a) is preferably 0.3 μm or more, preferably 0.4 μm or more, and more preferably 0.5 μm or more. By limiting the thickness of the (a) layer to this range, a film free from defects such as warpage in which the mechanical properties of the (a) layer and the optical properties of the (b) layer are balanced can be obtained.

In the present invention, the thicknesses of the laminated layers (a) and (b) can be measured by cutting the film diagonally in the thickness direction and observing the composition distribution of polyimide.

The polyimide used in the layer (a) in the present invention is preferably a polyimide having a yellow index of 10 or less and a total light transmittance of 85% or more when it is individually formed into a film with a thickness of 25±2 μm. Furthermore, the polyimide-based CTE used in the layer (a) is preferably 25 ppm/K or less, more preferably 20 ppm/K or less, and the tensile breaking strength is preferably 120 MPa or more, further preferably 140 MPa or more, The elongation at break is preferably 8% or more, more preferably 10% or more. As a preferable polyimide of the layer (a), a polyimide having a chemical structure obtained by polycondensation of the following tetracarboxylic anhydride and the following diamine can be exemplified: containing 70 mol% or more of lipid Tetracarboxylic anhydrides of cyclic tetracarboxylic anhydrides; and diamines containing diamines having an amide bond in the molecule of more than 70 mol%. Moreover, as the polyimide used for the layer (a), a polyimide having a chemical structure obtained by polycondensation of the following tetracarboxylic anhydride and the following diamine can be exemplified: containing 70 mol% or more of aromatic Tetracarboxylic anhydrides of the family of tetracarboxylic anhydrides; and diamines containing more than 70 mol% of diamines having a trifluoromethyl group in the molecule. Coloring can be suppressed by setting it as such a structure.

As the diamine having an amide bond in the molecule, 4-amino-N-(4-aminophenyl)benzylamide is preferable. The diamine having an amide bond is preferably 70 mol% or more, 80 mol% or more, and more preferably 90 mol% or more in the total diamine. In addition, as the diamine having a trifluoromethyl group in the molecule, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 1,4-bis(4-amine 2-trifluoromethylphenoxy)benzene and 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether are preferred. When using these diamine compounds having a fluorine atom in the molecule, especially a diamine having a trifluoromethyl group in the molecule, the usage amount is preferably 70 mol % or more in the total diamine, 80 mol % or more. It is preferable to use it at 90 mol% or more, more preferably at 90 mol% or more.

The polyimide used in the layer (b) in the present invention is preferably a polyimide having a yellow index of 5 or less and a total light transmittance of 90% or more when it is individually formed into a film with a thickness of 25±2 μm. As the polyimide used in the layer (b), a polyimide having a chemical structure obtained from the following tetracarboxylic anhydride and the following diamine can be exemplified: containing 70 mol% or more of an aromatic tetracarboxylic anhydride tetracarboxylic anhydride; and diamines containing at least 70 mol% of diamines having sulfur atoms in the molecule. Moreover, as the polyimide suitable for the (b) layer, a polyimide having a chemical structure obtained by polycondensation of the following tetracarboxylic anhydride and the following diamine can be exemplified: Tetracarboxylic acid anhydride containing trifluoromethyl tetracarboxylic acid in the molecule; and diamine containing diamine with trifluoromethyl group at least in the molecule more than 70 mol%.

As the aromatic tetracarboxylic acid anhydride of polyimide preferably used in layer (b), 4,4'-oxydiphthalic acid, pyromellitic acid, 3,3',4,4 '-Biphenyltetracarboxylic acid is preferred. The aromatic tetracarboxylic dianhydride used in the polyimide of the layer (b) is preferably 70 mol% or more of the total tetracarboxylic acid of the polyimide of the layer (b), more preferably 80 mol% % or more, more preferably 90 mol % or more, still more preferably 95 mol % or more. Heat resistance is improved by limiting the content of the aromatic tetracarboxylic acid to a predetermined range.

4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid is used as the polyimide used in the layer (b) as a tetracarboxylic acid containing a trifluoromethyl group in the molecule. Dianhydride is preferred. The tetracarboxylic acid containing trifluoromethyl group in the molecule of the polyimide used in the (b) layer is preferably 30 mol% or more of the total tetracarboxylic acid of the polyimide in the (b) layer, more Preferably it is 45 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more. By limiting the content of the trifluoromethyl tetracarboxylic acid in the molecule to a predetermined range, the colorless transparency is improved.

In the polyimide preferably used as the layer (b) of the present invention, the diamine preferably used is a diamine having at least a sulfo group in the molecule and/or a trifluoromethyl group in the molecule The diamine. As the diamine having a sulfo group in the molecule, 3,3'-diaminodiphenylene, 3,4'-diaminodiphenylene, and 4,4'-diaminodiphenylene can be used. In the present invention, by using a diamine containing a diamine having a sulfo group in the molecule in an amount of 70 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more, even with an aromatic Colorless transparency can also be obtained in the case of a combination of group tetracarboxylic anhydrides. As the diamine having a trifluoromethyl group, there are 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 1,4-bis(4-amino-2-triamine) Fluoromethylphenoxy)benzene and 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether are preferred. The usage-amount of the diamine which has a trifluoromethyl group in a molecule|numerator is preferably 70 mass % or more in all diamine, 80 mass % or more, and more preferably 90 mass % or more.

In the present invention, the polyimide of the layer (a) and the polyimide of the layer (b) are characterized by the yellowness index, total light transmittance, mechanical properties, etc. when the film with a thickness of 25±2 μm is separately formed. . Here, the operation of forming a thin film with a thickness of 25±2 μm alone is an evaluation on a scale that can be carried out in a laboratory, and is the value obtained by evaluating the following film: the solution of the polyimide or the polyimide precursor. The solution is applied to a glass plate with a size of 10 cm square, preferably 20 cm square or more, first pre-heated at a temperature of 120°C, pre-heated and dried until the residual solvent content becomes 40% by mass or less of the coating film, and then the solution is heated in nitrogen, etc. The resulting film was heated at 300°C for 20 minutes in an inert gas. When an inorganic component such as a slip agent and a filler is contained in order to adjust the physical properties, the values of the physical properties of the film obtained by using the solution containing these are used.

In the present invention, the polyimide of the (a) layer and the polyimide of the (b) layer may contain a slip agent (filler), respectively. As the slip agent, either inorganic fillers or organic fillers may be used, but inorganic fillers are preferred. The slip agent is not particularly limited, and examples thereof include silicon dioxide, carbon, ceramics, and the like, among which silicon dioxide is preferred. These slip agents may be used alone or in combination of two or more. The average particle size of the slip agent is preferably 10 nm or more, more preferably 30 nm or more, and further preferably 50 nm or more. Moreover, 1 micrometer or less is preferable, 500 nm or less is more preferable, and 100 nm or less is further more preferable. The content of the slip agent in the polyimide of the layer (a) and the polyimide of the layer (b) is preferably 0.01 mass % or more. From the viewpoint of improving the smoothness of the polyimide film, it is more preferably 0.02 mass % or more, still more preferably 0.05 mass % or more, and particularly preferably 0.1 mass % or more. Moreover, from a viewpoint of transparency, 30 mass % or less is preferable, 20 mass % or less is more preferable, 10 mass % or less is further more preferable, and 5 mass % or less is especially preferable.

Hereinafter, a preferred manufacturing method for obtaining the multilayer polyimide film of the present invention will be described. The manufacturing method of the multi-layer polyimide film of the present invention can preferably be produced through the following steps in the atmosphere or inert gas with a temperature of 10°C to 40°C and a humidity of 10% to 55%: 1: the step of coating (a) the polyimide solution or polyimide precursor solution for layer formation on the temporary support to obtain the coating film a1; 2: within 100 seconds after the coating film a1 is made, the polyimide solution or the polyimide precursor solution for layer formation (b) is applied to the coating film a1 to obtain the coating film ab1 The step of; 3: drying the above-mentioned coating film ab1, and heating for 5 minutes or more and 45 minutes or less until the residual solvent amount on the basis of the whole layer of the coating film ab1 becomes 15 mass % or more and 40 mass % or less, and the coating film ab2 is obtained; 4: the step of peeling off the aforementioned coating film ab2 from the temporary support to obtain a self-supporting film (coating film ab2); 5: Hold both ends of the aforementioned self-supporting film (coating film ab2), and further heat in a temperature range of 150°C or more and less than 200°C until the residual solvent amount on the basis of the entire coating film ab2 becomes 5% by mass or more 15 mass%, the step of obtaining the coating film ab3; 6: The above-mentioned heating step is continued, and the step of further heating until the residual solvent amount on the basis of the whole layer of the coating film ab3 becomes 0.5 mass % or less. The aforementioned temporary support system is preferably long and flexible. In addition, the residual solvent amount on the basis of the whole layer in the third step was determined only from the mass of the coating film ab1, and did not include the mass of the temporary support. In addition, the starting point of 100 seconds in the second step is (a) after the application of the polyimide solution or the polyimide precursor solution for layer formation to the temporary support is completed. The same applies to the following operations.

By peeling from the temporary support at the stage of the self-supporting film, by-products generated by drying and chemical reaction can be quickly discharged from the film.

In the present invention, the temperature is preferably 10°C or higher and 40°C or lower, preferably 15°C or higher and 35°C or lower, and the humidity is 10%RH or higher and 55%RH or lower, preferably 20%RH or higher and 50%RH in the atmosphere or The coating of the polyimide solution or the polyimide precursor solution is carried out on a long and flexible temporary support in an inert gas. Furthermore, it is preferable to apply the next layer within 100 seconds, preferably within 50 seconds, and more preferably within 25 seconds after coating the layer before one step. The time until the next layer is applied is preferably as fast as possible, and therefore the lower limit is not particularly limited, but industrially, it may be 1 second or more, and 2 seconds or more may be acceptable. As a coating method, the first layer can be coated by a comma coater, bar coater, slot coater, etc., and the second layer can be coated by a die coater, curtain coater, sprayer, or the like. Also, these multiple layers can also be applied practically simultaneously by using a multi-layer die.

The environment of the coating solution is preferably the atmosphere or an inert gas. The inert gas can be interpreted as a gas having a substantially low oxygen concentration, and from an economical point of view, nitrogen gas or carbon dioxide may be used.

The solvent used in the polyimide solution or polyimide precursor solution is mostly hygroscopic. If the solvent absorbs moisture and the water content of the solvent increases, the solubility of the resin component will decrease, and it will dissolve into the solution. A rapid increase in the viscosity of the solution occurs. If this happens after coating, the formation of a transition layer of an appropriate thickness is hindered. The precipitation of such dissolved components can be sufficiently prevented by controlling the humidity within a predetermined range within a period of about 100 seconds.

As the temporary support used in the present invention, glass, metal plate, metal tape, metal cylinder, polymer film, metal foil, etc. can be used. In the present invention, a long and flexible temporary support is preferably used, and films such as polyethylene terephthalate, polyethylene naphthalate, and polyimide can be used as the temporary support. It is one of the preferred aspects to apply a mold release treatment to the surface of the temporary support.

In the present invention, after coating all the layers, drying is performed by heat treatment and required chemical reactions are performed. In the case of using the polyimide solution, only drying is required for the purpose of removing the solvent, but in the case of using the polyimide precursor solution, both drying and chemical reaction are required. Here, the polyimide precursor is preferably in the form of polyimide or polyisoimide. Dehydration condensation is required to convert polyamides into polyimides. The dehydration condensation reaction can be carried out only by heating, but an imidization catalyst can also be used as necessary. In the case of polyisoimide, it can also be converted from isoimide bonds to imide bonds by heating. In addition, an appropriate catalyst may be used in combination. The residual solvent amount of the final thin film is 0.5 mass % or less, preferably 0.2 mass % or less, more preferably 0.08 mass % or less, based on the average value of the entire film layer. The heating time is preferably 5 minutes or more and 60 minutes or less, preferably 6 minutes or more and 50 minutes or less, and more preferably 7 minutes or more and 30 minutes or less. By limiting the heating time to a predetermined range, the removal of the solvent and the necessary chemical reaction can be completed, and the warpage of the film can be reduced, and the colorless transparency and mechanical properties (especially elongation at break) can be maintained at a high level. When the heating time is short, the warpage of the film becomes large, and if the heating time is longer than necessary, the coloring of the film becomes stronger and the elongation at break of the film decreases.

In the present invention, as long as the applied solution can be dried by heating or chemically reacted and can be peeled off from the temporary support due to self-support, it can also be peeled off from the temporary support in the middle of the heating step. More specifically, it takes 5 minutes or more and 45 minutes or less, preferably 6 minutes or more and 30 minutes or less, more preferably 7 minutes or more and 20 minutes or less, until the average residual solvent amount of the whole film layer reaches 15% by mass. The self-supporting film is peeled off from the temporary support after the above range of 40 mass %. The peeled self-supporting film is in a state in which drying of the layer (a) sandwiched between the temporary support and the layer (b) has not progressed relative to the layer (b) in contact with air or an inert gas. In this state, the two ends of the self-supporting film are held by holding the ends of the self-supporting film with a clip or poking a needle, and conveyed in a heating environment, and further heated in a temperature range of 150°C or more and less than 200°C until The step of making the residual solvent amount on the basis of the whole layer to be 5% by mass or more and 15% by mass can realize rapid drying of the inside and the outside at the same time. By applying rapid drying, a film with reduced warpage of the film and further reduced CTE can be obtained as compared with the case where the drying temperature is 150° C. or lower. According to the conjecture of the inventors, it is assumed that the mechanism for obtaining such an effect is that the solvent remains in such a way that the residual solvent amount becomes 5% by mass to 15% by mass during heating at 150°C or more and less than 200°C. Layer (a) Compared with the layer (b), there are more residual components of the solvent. Therefore, it is considered that the arrangement of the polymer chains of the layer (a) is disordered due to the presence of the solvent, so that the CTE becomes slightly larger than that without this step. On the other hand, it is presumed that the residual component of the solvent in the layer (b) is relatively small, so that the disorder of the arrangement of the polymer chains in the layer (b) is less likely to occur, and as a result, the CTE can be reduced. It is considered that the difference in CTE between the two layers becomes smaller than the difference originally manifested by this, and it is considered to be related to the effect of reducing the warpage when it becomes a laminated film. Also, it is believed that layer (b) can reduce CTE by going through this step compared to not going through this step. It is considered that the reduction in the CTE of the layer (b), which accounts for the majority of the laminated film in terms of thickness ratio, is related to the effect of reducing the CTE of the entire laminated film as a result.

The present invention can also extend the aforementioned self-supporting film. The stretching may be either of the film longitudinal direction (MD direction) and the film width direction (TD), or both. The stretching in the longitudinal direction of the film can be performed using the speed difference between the conveying rollers or the speed difference between the conveying rollers and the both ends being held. The extension in the width direction of the film can be carried out by spreading between the holding clips or needles. Extending and heating can also be performed simultaneously. The stretching ratio can be arbitrarily selected between 1.00 times and 2.5 times. In the present invention, a polymer of a composition that is difficult to stretch (ie, prone to fracture due to stretching) is combined by combining a polyimide that is difficult to stretch alone and a polyimide that is stretchable by making the film into a multilayer structure. Imide also becomes extensible, which can improve mechanical properties. In addition, the volume of the polyimide is reduced in the middle of film formation due to drying or dehydration condensation, and the stretching effect is exhibited even in the state where both ends are held at equal intervals (the stretching ratio is 1.00 times).

In the multilayer polyimide film of the present invention, the layers (a) and (b) are preferably added to polyimide containing a slip agent and the like to impart fine irregularities on the surface of the layer (film), thereby improving the film's properties. Sliding, etc. It is preferable that the slip agent is added only to the layer (a) which becomes the outer layer. As the slip agent, inorganic or organic fine particles having an average particle diameter of about 0.03 μm to 3 μm can be used. Specific examples include titanium oxide, aluminum oxide, silicon dioxide, calcium carbonate, calcium phosphate, and calcium hydrogen phosphate. , calcium pyrophosphate, magnesium oxide, calcium oxide, clay minerals, etc. The content of the slip agent is preferably 0.1% by mass or more in the polyimide (polymer), more preferably 0.4% by mass or more. Moreover, 50 mass % or less is preferable, and 30 mass % or less is more preferable. [Example]

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In addition, each physical property value etc. in a manufacture example and an Example were measured by the following method.

<Thickness measurement of polyimide film> Measured using a micrometer (Millitron 1245D manufactured by Feinpruf).

<tensile elastic modulus, tensile strength (breaking strength), and breaking elongation> The film cut out a rectangle of 100 mm×10 mm in the flow direction (MD direction) and the width direction (TD direction) at the time of coating, respectively, and was used as a test piece. Using a tensile testing machine (manufactured by Shimadzu Corporation, Autograph(R) model name AG-5000A), under the conditions of a tensile speed of 50 mm/min and a distance between the clamps of 40 mm, the tensile elastic modulus was obtained for the MD direction and the TD direction, respectively. The average value of the measured values in the MD direction and the TD direction was obtained from the number, tensile strength and elongation at break.

<Coefficient of Linear Expansion (CTE)> In the flow direction (MD direction) and the width direction (TD direction) of the film at the time of coating, the expansion and contraction ratio was measured under the following conditions, and the measurement was performed at intervals of 15°C such as 30°C to 45°C and 45°C to 60°C. The expansion ratio/temperature was measured until 300° C., the average value of all measured values was calculated as CTE, and the average value of the measured values in the MD direction and the TD direction was further obtained. Machine name: TMA4000S manufactured by MAC Science Corporation Sample length: 20mm Sample width: 2mm Heating start temperature: 25℃ Heating end temperature: 300℃ Heating rate: 5℃/min Gas environment: Argon

＜Film thickness＞ A chamfered section of the film was made by SAICAS DN-20S type (DAIPLA WINTES), and then the chamfered section was subjected to a micro-IRCary 620 FTIR (Agilent) using a micro-ATR using germanium crystals (incidence angle 30°). The spectrum is obtained by the method, and the ratio of the film thickness of (b) layer/(a) layer film thickness is obtained from the increase and decrease of the characteristic peaks of the layers (a) and (b) and the calibration curve obtained in advance. The thickness in the range of more than 25 times.

＜Haze＞ The haze of the film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Corporation). A D65 lamp was used as the light source. Moreover, the same measurement was performed three times, and the arithmetic mean value was used.

<Total light transmittance> The total light transmittance (TT) of the film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Corporation). A D65 lamp was used as the light source. Moreover, the same measurement was performed three times, and the arithmetic mean value was used. The results are shown in Tables 1 and 2.

＜Yellow index＞ Using a colorimeter (ZE6000, manufactured by Nippon Denshoku Co., Ltd.) and a C2 light source, the tristimulus value XYZ value of the film was measured according to ASTM D1925, and the yellowness index (YI) was calculated by the following formula. Moreover, the same measurement was performed three times, and the arithmetic mean value was used. YI=100×(1.28X−1.06Z)/Y

＜Warpage of film＞ A film cut into a square with a size of 100 mm × 100 mm was used as a test piece, and the test piece was placed in a concave shape at room temperature on a flat surface, and the distances from the four corners to the flat surface (h1rt, h2rt, h3rt, h4rt) were measured. : unit mm), and the average value was taken as the warpage amount (mm).

[Production Example 1: (a) Production of a slip agent-containing polyamic acid solution As for layer formation] After nitrogen substitution was carried out in a reaction vessel equipped with a nitrogen gas introduction tube, a reflux tube, and a stirring bar, 22.73 parts by mass of 4,4'-diaminobenzylaminobenzene (DABAN) was dissolved in 201.1 parts by mass of N,N -Dimethylacetamide (DMAc), and then 19.32 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was added in batches in a solid state, and then at room temperature Stir for 24 hours. Then, 173.1 parts by mass of DMAc was added and diluted to obtain a polyamic acid solution of 10 mass % of NV (solid content) and a reduced viscosity of 3.10 dl/g. To the obtained polyamic acid solution, the silica (slip agent) was further added so that the total amount of the polymer solid content in the polyamic acid solution was 1.4% by mass, and colloidal silica was dispersed in two. A dispersion of methylacetamide (“SNOWTEX (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industry Co., Ltd.) was used as a slip agent to obtain a homogeneous polyamide solution As.

[Production Example 2: (a) Production of a slip agent-containing polyamic acid solution Bs for layer formation)] After nitrogen substitution was carried out in a reaction vessel equipped with a nitrogen introduction tube, a reflux tube, and a stirring bar, 32.02 parts by mass of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB ) dissolved in 279.9 parts by mass of N,N-dimethylacetamide (DMAc), and then 20.59 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 9.31 mass parts of After each portion of 4,4'-oxydiphthalic dianhydride (ODPA) was added in portions in a solid state, it was stirred at room temperature for 24 hours. Then, a solid content of 17 mass % and a reduced viscosity of 3.60 dl/g of a polyamic acid solution were obtained. In the polyamic acid solution, silica (slip agent) was added so that the total amount of polymer solids in the polyamic acid solution was 0.45% by mass, and colloidal silica was dispersed in dimethyl ethyl acetate. A dispersion of amide (“SNOWTEX (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industry Co., Ltd.) was used as a slip agent to obtain a homogeneous polyamide solution Bs.

[Production Example 3: (a) Production of a slip agent-containing polyamic acid solution Cs for layer formation)] After nitrogen substitution was carried out in a reaction vessel equipped with a nitrogen introduction tube, a reflux tube, and a stirring bar, 32.02 parts by mass of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB ) was dissolved in 279.9 parts by mass of N,N-dimethylacetamide (DMAc), and then 29.42 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added to the solid After being added in batches, the mixture was stirred at room temperature for 24 hours. Then, a solid content of 17 mass % and a reduced viscosity of 3.80 dl/g of a polyamic acid solution were obtained. In the polyamic acid solution, silica (slip agent) was added so that the total amount of the polymer solid content in the polyamic acid solution was 0.5% by mass, and colloidal silica was dispersed in dimethyl ethyl acetate. A dispersion of amide (“SNOWTEX (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industry Co., Ltd.) was used as a slip agent to obtain a homogeneous polyamide solution Cs.

[Production Example 4: (b) Production of Polyimide Solution D for Layer Formation] 32.02 parts by mass of 2,2'-bis(trifluoromethyl)-4,4'-bis was added to a reaction vessel equipped with a nitrogen gas introduction tube, a Dean-Stark apparatus, a reflux tube, a thermometer, and a stirring bar while introducing nitrogen gas. aminobiphenyl (TFMB) and 230 parts by mass of N,N-dimethylacetamide (DMAc) were completely dissolved, and then 44.42 parts by mass of 4,4'-(2,2-hexafluoro) After isopropylidene)diphthalic dianhydride (6FDA) was added in batches in a solid state, it was stirred at room temperature for 24 hours. Then, the solid content of 25 mass % and the reduction viscosity of 1.10 dl/g of polyamic acid solution Daa were obtained. Next, after adding 204 mass parts of DMAc to the obtained polyamic acid solution Daa and diluting so that the concentration of polyamic acid might become 15 mass %, 1.3 mass parts of isoquinolines were added as an imidization accelerator. Next, 12.25 parts by mass of acetic anhydride was slowly dropped as an imidizing agent while stirring the polyamic acid solution. Then, stirring was continued for 24 hours, chemical imidization reaction was performed, and the polyimide solution Dpi was obtained. Next, when 100 parts by mass of the obtained polyimide solution Dpi was moved to a reaction vessel equipped with a stirring device and a stirrer, and 150 parts by mass of methanol was slowly dropped while stirring, the precipitation of powdery solid was confirmed. Then, the powder of the content of the reaction vessel was dehydrated and filtered, washed with methanol, vacuum-dried at 50° C. for 24 hours, and further heated at 260° C. for 5 hours to obtain polyimide powder Dpd. Polyimide solution D was obtained by dissolving 20 parts by mass of the obtained polyimide powder in 80 parts by mass of DMAc.

[Production Example 5: (b) Production of Polyimide Solution E for Layer Formation] 120.5 parts by mass of 4,4'-diaminodiphenylene (4,4'-DDS) was added to a reaction vessel equipped with a nitrogen gas introduction tube, a Dean-Stark apparatus, a reflux tube, a thermometer, and a stirring bar while introducing nitrogen gas. , 51.6 parts by mass of 3,3'-diaminodiphenylene (3,3'-DDS), and 500 parts by mass of γ-butyrolactone (GBL). Next, 217.1 parts by mass of 4,4'-oxydiphthalic dianhydride (ODPA), 223 parts by mass of GBL, and 260 parts by mass of toluene were added at room temperature, and the temperature was raised to an internal temperature of 160° C. Heating and refluxing was performed at °C for 1 hour to carry out imidization. After the imidization was completed, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed, the temperature was returned to room temperature, and GBL was added so that the solid content might be 20% by mass concentration, and a polyimide solution E was obtained.

[Production Example 6: (b) Production of Polyamic Acid Solution F for Layer Formation] After nitrogen substitution was carried out in a reaction vessel equipped with a nitrogen introduction tube, a reflux tube, and a stirring bar, 33.36 parts by mass of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) was added. ), 336.31 parts by mass of N-methyl-2-pyrrolidone (NMP) to completely dissolve, and then 9.81 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) , 11.34 parts by mass of 3,3',4,4'-biphenyltetracarboxylic acid and 4.85 parts by mass of (ODPA) were added in batches in a solid state, respectively, followed by stirring at room temperature for 24 hours. Then, a polyamide solution F with a solid content of 15% by mass and a reduced viscosity of 3.50 dl/g was obtained (molar ratio of TFMB//CBDA/BPDA/ODPA=1.00//0.48/0.37/0.15).

[Production Example 7: (b) Production of a slip agent-containing polyamic acid solution Fs for layer formation)] After nitrogen substitution was carried out in a reaction vessel equipped with a nitrogen introduction tube, a reflux tube, and a stirring bar, 33.36 parts by mass of 2,2'-bis(trifluoromethyl)benzidine (TFMB) and 270.37 parts by mass of N-methyl A dispersion of 2-pyrrolidone (NMP) and colloidal silica in dimethylacetamide (“SNOWTEX (registered trademark) DMAC-ST”, manufactured by Nissan Chemical Industry Co., Ltd.) is made of silica. The total amount of the polymer solid content in the polyamic acid solution was added so as to be 30.0% by mass to completely dissolve it, and then 9.81 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added. (CBDA), 11.34 parts by mass of 3,3',4,4'-biphenyltetracarboxylic acid, and 4.85 parts by mass of (ODPA) were added in batches in a solid state, followed by stirring at room temperature for 24 hours. Then, 165.7 parts by mass of DMAc was added and diluted to obtain a polyamide solution Fs with a solid content of 18% by mass and a reduced viscosity of 2.7 dl/g (molar ratio of TFMB//CBDA/BPDA/ODPA=1.00//0.48/ 0.37/0.15).

The polyimide solutions and polyimide solutions (polyimide precursor solutions) obtained in Production Examples 1 to 7 were thinned by the following methods, and optical properties and mechanical properties were measured. The results are shown in Table 1. (Method for obtaining a film for measuring physical properties alone) A bar coater was used to coat a polyimide solution or a polyamide solution with a final thickness of 25±2 μm on an area of about 20 cm square in the center of a 30 cm glass plate, and the inert nitrogen gas flowed and dried in a quiet manner. The oven was heated at 100° C. for 30 minutes, and after confirming that the residual solvent content of the coating film was 40% by mass or less, it was heated at 300° C. for 20 minutes in a Mongolian furnace replaced with dry nitrogen. Next, it was taken out from the furnace, and one end of the dried coating film (film) was lifted up with a utility knife, and the film was carefully peeled off from the glass to obtain a film.

(Example 1) The non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) was applied in an atmosphere conditioned at 25°C and 45% RH using a notch wheel coater. Above, the polyamide solution As obtained in Production Example 1 was applied so that the final film thickness was 2.3 μm, and then 10 seconds later, the polyamide solution As was applied on the polyamide solution As so that the final film thickness was 22.7 μm by means of a mold. The polyimide solution D obtained in Production Example 4 was applied by using a coater. It was dried at 100°C for 10 minutes. The self-supporting film obtained after drying is peeled off from the A4100 film as a support, and the end of the film is held by inserting the needles through a pin tenter with a pin card blade equipped with needles so that the film does not break. Adjust the interval between the needle-comb pieces and convey them in a way that does not cause unnecessary sagging, and heat them under the conditions of 3 minutes at 150 °C, 3 minutes at 200 °C, 3 minutes at 250 °C, and 6 minutes at 300 °C to make The imidization reaction proceeds. After that, it was cooled to room temperature for 2 minutes, and the portions with poor flatness at both ends of the film were cut out with a cutter, and wound into a roll to obtain a film roll with a width of 580 mm and a length of 100 m. Table 2 shows the evaluation results of the obtained thin films.

(Examples 2 to 9) The following conditions were set as shown in Examples 2 to 8 in Table 2 to obtain films, respectively. The results of the same evaluation are shown in Table 2.

(Comparative Example 1) The non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) was applied in an atmosphere conditioned at 25°C and 45% RH using a notch wheel coater. Above, the polyamide solution As obtained in Production Example 1 was applied so that the final film thickness would be 5.0 μm, and after 10 seconds, the polyamide solution As was applied on the polyamide solution As so that the final film thickness would be 20.0 μm by means of a mold. The polyimide solution D obtained in Production Example 4 was applied by using a coater. It was dried at 100°C for 10 minutes. The self-supporting film obtained after drying is peeled off from the A4100 film as a support, and the end of the film is held by inserting the needles through a pin tenter with a pin card blade equipped with needles so that the film does not break. Adjust the interval between the needle-comb pieces and convey them in a way that does not cause unnecessary sagging, and heat them under the conditions of 3 minutes at 150 °C, 3 minutes at 200 °C, 3 minutes at 250 °C, and 6 minutes at 300 °C to make The imidization reaction proceeds. After that, it was cooled to room temperature for 2 minutes, and the portions with poor flatness at both ends of the film were cut out with a cutter, and wound into a roll to obtain a film roll with a width of 580 mm and a length of 100 m. Table 2 shows the evaluation results of the obtained thin films.

(Comparative Example 2) Except that the polyamic acid solution As of Comparative Example 1 was changed to the polyamic acid solution Bs, and the coating was applied so that the final film thickness was 0.8 μm, and then 10 seconds later, the final film was applied on the polyamic acid solution Bs. Except that the polyimide solution D obtained in Production Example 4 was coated with a die coater so that the thickness was 24.2 μm, the same operation as in Comparative Example 1 was performed to obtain a film roll having a width of 580 mm and a length of 100 m. Table 2 shows the evaluation results of the obtained thin films.

(Comparative Example 3) Except that the polyamic acid solution As of Comparative Example 1 was changed to the polyamic acid solution Cs, the coating was applied so that the final film thickness was 0.2 μm, and then the final film was applied on the polyamic acid solution Cs after 10 seconds. Except that the polyimide solution D obtained in Production Example 4 was coated with a die coater so that the thickness was 4.8 μm, the same operation as in Comparative Example 1 was performed to obtain a film roll with a width of 580 mm and a length of 100 m. Table 2 shows the evaluation results of the obtained thin films.

As is clear from Table 2, in Examples 1 to 9, the warpage became less than 5 mm and the CTE became less than 45 ppm/K, and a good multilayer polyimide film was obtained. On the other hand, in Comparative Examples 1 to 3, the warpage was 5 mm or more, or the CTE was more than 45 ppm/K.

[Table 1] Polyimide (PI) solution or polyamide acid (PAA) solution Manufacturing Example 1 Manufacturing example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 (a) For layer (a) For layer (a) For layer (b) For layer (b) For layer (b) For layer (b) For layer PAA solution As PAA solution Bs PAA solution Cs PI solution D PI solution E PAA solution F PAA solution Fs Acid content molar % 6FDA - - - 100 - - - ODPA - 30 - - 100 15 15 CBDA 100 - - - - 48 48 BPDA - 70 100 - - 37 37 Diamine Composition Molar % TFMB - 100 100 100 - 100 100 44DDS - - - - 70 - - 33DDS - - - - 30 - - DABAN 100 - - - - - - Inorganic filler (slip agent) (% by mass of polymer) _SiO2 1.4 0.45 0.5 - - - 30.0 membrane thickness μm 25 25 25 25 25 25 25 haze % 0.67 0.65 0.6 0.28 0.31 0.3 0.4 total light transmittance % 85.2 86.5 86.4 90.3 92.4 89.1 90.3 yellow index 6.8 8.3 3.5 1.3 2.3 3.8 3.7 Breaking strength MPa 162 166 140 134 126 151 87 Elongation at break % 14.2 12.5 10.2 22.6 18.4 8.3 1.6 elastic modulus GPa 3.8 3.5 3.7 3.7 3.5 4.7 6.8 CTE ppm/K 17 25 twenty four 48 51 37 32

[Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Layer composition solution name (thickness μm) (b) layer D D D D E E E F Fs D D D (a) layer - basal plane As Bs Cs Cs As Bs Cs As As As Bs Cs temporary support PET PET PET PET PET PET PET PET PET PET PET PET Coating environment temperature and humidity °C, %RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH 25℃ 45%RH Primary heating temperature °C 100 100 100 100 100 100 100 100 100 100 100 100 One heating time minute 10 10 10 10 10 10 10 10 10 10 10 10 Residual solvent amount quality% twenty four 19 33 33 19 37 32 twenty four 20 twenty four 19 33 Secondary heating temperature °C 150 150 150 150 150 150 150 150 150 150 150 150 Secondary heating time minute 3 3 3 3 3 3 3 3 3 3 3 3 Residual solvent amount quality% 5.4 6.5 9.0 9.0 8.0 9.0 9.0 8.5 7.5 5.4 6.5 9.0 final heating temperature °C 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 200-250-300 final heating time minute 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 3-3-6 total film thickness μm 25 25 25 7.5 25 25 25 25 25 25 25 5 Amount of residual solvent after final heating % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 haze % 0.3 0.3 0.3 0.3 0.3 0.4 0.3 0.4 0.4 0.4 0.3 0.3 total light transmittance % 89.8 90.1 89.7 90.0 92.1 91.1 91.9 88.5 90.1 89.3 90.1 90.3 yellow index 1.8 1.6 1.7 1.4 2.5 3.3 2.4 4.3 3.8 2.4 1.5 1.4 Breaking strength MPa 136.5 135.2 135.0 131.0 127.4 132.7 127.3 152.8 89.9 139.6 135.0 130.0 Elongation at break % 21.8 22.2 20.5 22.0 18.2 17.4 17.7 9.3 2.1 20.9 22.3 21.7 elastic modulus GPa 3.7 3.7 3.7 3.7 3.5 3.5 3.5 4.6 6.7 3.7 3.7 3.7 CTE ppm/K 39.2 40.8 38.3 44.2 43.7 39.5 42.7 29.7 28.4 41.8 47.0 47.2 warping mm 2.8 1.3 3.9 0.9 2.0 4.7 2.4 3.7 1.0 7.5 1.1 0.5 (a) Layer thickness μm 2.3 1.0 4.2 0.3 1.0 4.2 2.3 4.2 1.0 5.0 0.8 0.2 (b) Layer thickness μm 22.7 24.0 20.8 7.2 24.0 20.8 22.7 20.8 24.0 20.0 24.2 4.8 (b)/(a) Thickness ratio 10 25 5 25 25 5 10 5 25 4 30 25 [Possibility of Industrial Use]

As described above, the multi-layer polyimide film of the present invention exhibits good optical and mechanical properties compared to the case where polyimides of different compositions are individually thinned. In addition, according to the production method of the present invention, even a laminate of polyimides having different compositions divided into multiple layers and functionally shared can be formed into a thin film that is balanced with low CTE while suppressing warpage. The multilayer polyimide film of the present invention has excellent optical properties, colorless transparency, excellent mechanical properties, and exhibits low CTE, so it can be used as a flexible and lightweight display device component, or can be used in Switch elements such as touch panels, pointing devices, and the like that require transparency.

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Claims (5)

A multi-layer polyimide film, which is a multi-layer polyimide film comprising at least a polyimide layer (a) layer and a polyimide layer (b) layer, wherein The polyimide layer (a) and the polyimide layer (b) have different compositions, The film thickness of the polyimide layer (a) is 0.3 μm or more, The film thickness of the polyimide layer (b) is not less than 5 times and not more than 25 times the film thickness of the polyimide layer (a), The multilayer polyimide film has a thickness of 3 μm or more and 120 μm or less, a yellowness index of 5 or less, and a total light transmittance of 86% or more. The multilayer polyimide film of claim 1, wherein the (a) layer and the (b) layer are respectively mainly composed of polyimide with the following characteristics; Layer (a): Polyimide with a yellow index of 10 or less and a total light transmittance of 85% or more when it is individually made into a film with a thickness of 25±2 μm (b) Layer: Polyimide having a yellow index of 5 or less and a total light transmittance of 90% or more when it is individually formed into a thin film with a thickness of 25±2 μm. The multilayer polyimide film of claim 1 or 2, wherein the polyimide of the (a) layer comprises a polyimide of chemical structure obtained by polycondensation of tetracarboxylic anhydride and diamine, The tetracarboxylic anhydride contains at least one selected from the group consisting of an alicyclic tetracarboxylic anhydride, an aromatic tetracarboxylic anhydride having an ether group in the molecule, and an aromatic tetracarboxylic anhydride having a biphenyl group in the molecule tetracarboxylic anhydride, The diamine contains at least one diamine selected from the group consisting of a diamine having an amide bond in the molecule and a diamine having a trifluoromethyl group in the molecule. The multilayer polyimide film of any one of claims 1 to 3, wherein the polyimide of the (b) layer comprises a polyimide of chemical structure obtained by polycondensation of tetracarboxylic anhydride and diamine , The tetracarboxylic anhydride is selected from the group consisting of an alicyclic tetracarboxylic anhydride, an aromatic tetracarboxylic anhydride having an ether group in the molecule, an aromatic tetracarboxylic anhydride having a biphenyl group in the molecule, and a trifluorocarbon in the molecule One or more tetracarboxylic anhydrides of the group of methyl aromatic tetracarboxylic anhydrides, The diamine contains at least one diamine selected from the group consisting of a diamine having a sulfo group in the molecule and a diamine having a trifluoromethyl group in the molecule. A method for producing a multilayer polyimide film as claimed in any one of claims 1 to 4, comprising at least: 1: the step of coating (a) the polyimide solution or polyimide precursor solution for layer formation on the temporary support to obtain the coating film a1; 2: within 100 seconds after the coating film a1 is made, the polyimide solution or the polyimide precursor solution for layer formation (b) is applied to the coating film a1 to obtain the coating film ab1 The step of; 3: the step of heating the coating film ab1 to obtain the coating film ab2 with a residual solvent content of 15-40 mass % on the basis of the whole coating film; 4: the step of peeling off the coating film ab2 from the temporary support; 5: heating the coating film ab2 at a temperature of 150°C or more and less than 200°C to obtain a coating film ab3 with a residual solvent content of 5% by mass or more and less than 15% by mass on the basis of the whole coating film; 6: A step of heating the coating film ab3 to obtain the coating film ab4 having a residual solvent content of 0.5 mass % or less on the basis of the entire coating film.