WO2017065319A1 - ポリイミド積層体及びその製造方法 - Google Patents
ポリイミド積層体及びその製造方法 Download PDFInfo
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- WO2017065319A1 WO2017065319A1 PCT/JP2016/080758 JP2016080758W WO2017065319A1 WO 2017065319 A1 WO2017065319 A1 WO 2017065319A1 JP 2016080758 W JP2016080758 W JP 2016080758W WO 2017065319 A1 WO2017065319 A1 WO 2017065319A1
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- Prior art keywords
- polyimide
- polyimide layer
- thermal expansion
- expansion coefficient
- layer
- Prior art date
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- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 1
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- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
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- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B7/04—Interconnection of layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Definitions
- the present invention relates to a polyimide laminate in which a first polyimide layer and a second polyimide layer are laminated on a support and a method for producing the same, and more specifically, a flexible resin comprising a second polyimide layer.
- the present invention relates to a polyimide laminate suitable for obtaining a display device having a display unit on a substrate and a method for producing the same.
- Display devices such as liquid crystal display devices and organic EL display devices are widely used from large displays such as televisions to small displays such as mobile phones, personal computers and smartphones.
- a thin film transistor TFT
- an electrode, a light emitting layer, an electrode and the like are sequentially formed, and finally airtightly sealed with a glass substrate and a multilayer thin film.
- the type of the display device is not particularly limited, but includes display device components such as a liquid crystal display device, an organic EL display device, electronic paper, and a color filter.
- the display device includes an organic EL lighting device, a touch panel device, a conductive film laminated with ITO, a gas barrier film that prevents permeation of moisture, oxygen, and the like, and components of a flexible circuit board.
- Various functional devices used are also included.
- the flexible device referred to in the present invention is not only a component such as a liquid crystal display device, an organic EL display device, and a color filter, but also an organic EL lighting device, a touch panel device, an electrode layer or a light emitting layer of the organic EL display device, A gas barrier film, an adhesive film, a thin film transistor (TFT), a wiring layer of a liquid crystal display device, or a transparent conductive layer is also included.
- Patent Document 1 relates to a polyimide useful as a plastic substrate for a flexible display and an invention relating to a precursor thereof, using tetracarboxylic acids containing an alicyclic structure such as cyclohexylphenyltetracarboxylic acid.
- tetracarboxylic acids containing an alicyclic structure such as cyclohexylphenyltetracarboxylic acid.
- the polyimide reacted with various diamines is excellent in transparency.
- attempts have been made to reduce the weight by using a flexible resin base instead of a glass substrate.
- an organic EL display device using highly transparent polyimide is used. Has been proposed.
- a resin film such as polyimide is useful as a support base material for a flexible display, but the manufacturing process of the display device has already been performed using a glass substrate, and its production equipment Most of them are designed on the assumption that glass substrates are used. Therefore, it is desirable to be able to produce display devices while effectively utilizing existing production equipment.
- the manufacturing process of a predetermined display device is completed in a state where the resin is laminated on the glass substrate, and then the glass substrate is removed to provide a display unit on the resin base material.
- a display device There are methods for manufacturing a display device (see Patent Documents 2 to 3 and Non-Patent Documents 3 to 4). In the case of such a method, it is important to separate the resin base material and the glass without damaging the display portion formed on the resin base material.
- Patent Document 3 and Non-Patent Document 3 after a predetermined display portion is formed on a resin base material applied and fixed on a glass substrate, a method called an EPLaR (Electronics on Plastic by Laser Release) process is used.
- the resin base material provided with the display part is forcibly separated from the glass substrate by irradiating a laser from the glass side.
- Patent Document 2 and Non-Patent Document 4 after a release layer is formed on a glass substrate, a polyimide resin is applied a little larger than the release layer to form a polyimide layer, and a cutting line reaching the release layer is inserted. Thus, a small polyimide film is peeled off from the release layer.
- the thermal expansion coefficient of the glass substrate is several ppm / K
- the resin generally has a thermal expansion coefficient of several tens of ppm / K or more.
- a resin solution is applied on the glass substrate and heated. When it is cured by treatment or the like to form a resin layer and allowed to cool to room temperature, warpage occurs. If such warpage cannot be suppressed, the subsequent formation of the display portion and the like will be adversely affected.
- the flexible display TFT substrate process usually uses In-Ga-Zn-O semiconductor (IGZO) or low-temperature polysilicon (LTPS) method, and heat of 350 ° C or higher multiply.
- IGZO In-Ga-Zn-O semiconductor
- LTPS low-temperature polysilicon
- the thermal expansion coefficient of the glass substrate is several ppm / K
- the resin generally has a thermal expansion coefficient of several tens of ppm / K or more, so that the laminate is warped, and the display unit There is a risk that it will not be possible to reduce the size.
- Patent Document 3 a resin layer (b) having a thermal expansion coefficient between the support substrate and the resin film (a) is provided between the support substrate and the resin film (a). Although disclosed, the effect of suppressing warpage is not sufficient.
- JP 2008-231327 A Japanese Patent No. 4834758 Japanese Patent No. 5408848
- the conventional glass substrate can be used as a part of the display device. From the viewpoint of reducing the thickness, weight, and flexibility, the applications of the display device can be further expanded. To that end, it is possible to easily separate the support represented by the glass substrate and the resin base material, and solve the problem of warpage in a state where the glass substrate and the resin base material are laminated. It becomes important to do.
- an object of the present invention is to provide a polyimide laminate in which warpage is suppressed and the resin base material can be easily and easily separated.
- Another object of the present invention is to provide a method for producing a polyimide laminate in which the occurrence of warpage is suppressed and the resin substrate can be easily and easily separated.
- a first polyimide layer having a specific composition having a thermal expansion coefficient larger than that of 5 to 30 ppm / K is provided on a support such as a glass substrate, and the thermal expansion coefficient is first on the first polyimide layer. It has been found that by providing a second polyimide layer having a specific composition equal to or higher than the polyimide layer, it is possible to obtain a laminate that suppresses the occurrence of warpage and to easily separate the resin base material. The present invention has been completed.
- the gist of the present invention is as follows.
- a laminate comprising a plurality of polyimide layers in the order of a first polyimide layer and a second polyimide layer on a support having a thermal expansion coefficient of 1 to 10 ppm / K,
- the film thickness of the first polyimide layer is 1 to 50 ⁇ m, the thermal expansion coefficient is not less than the thermal expansion coefficient of the support, is 5 to 30 ppm / k, and the glass transition temperature is not less than 300 ° C .
- the film thickness of the second polyimide layer is 5 to 30 ⁇ m, the thermal expansion coefficient is greater than or equal to the thermal expansion coefficient of the first polyimide layer, and the first polyimide layer and the second polyimide layer are A polyimide laminate characterized by being peelable.
- Y is an aromatic or alicyclic tetravalent organic group.
- a polyimide or polyimide precursor resin solution is applied and dried, and heat treatment is performed, so that the thermal expansion coefficient is greater than or equal to the thermal expansion coefficient of the support.
- a polyimide or polyimide precursor resin solution different from the above resin solution is applied and dried, and heat treatment is performed to increase the thermal expansion coefficient of the first polyimide layer.
- the present invention it is possible to obtain a polyimide laminate in which generation of warpage is suppressed and the second polyimide layer can be separated from the first and second polyimide layers laminated on the support. Therefore, for example, in obtaining a display device including a display unit on a resin base material made of the second polyimide layer, the predetermined display unit can be accurately and reliably formed on the second polyimide layer.
- the display device can be made thin, light, and flexible.
- the polyimide laminate in the present invention includes a support having a thermal expansion coefficient of 1 to 10 ppm / K.
- a support is made of an inorganic material, for example, generally a glass substrate having a thermal expansion coefficient of 1 to 10 ppm / K, a silicon wafer having a thermal expansion coefficient of 1 to 6 ppm / K, and also a thermal expansion coefficient.
- Stainless steel having a coefficient of 1 to 10 ppm / K, silicon carbide having a coefficient of thermal expansion of 1 to 10 ppm / K, and the like can be mentioned.
- a glass substrate or a silicon wafer is preferable.
- a first polyimide layer having a thermal expansion coefficient equal to or higher than that of the support and 5 to 30 ppm / K and having a glass transition temperature of 300 ° C. or higher is laminated on the support.
- the occurrence of warpage can be reliably suppressed.
- the presence of the first polyimide layer can increase the degree of freedom in designing the second polyimide layer described later.
- the glass transition temperature of the first polyimide layer may be 300 ° C. or higher, but is preferably 320 ° C. or higher because the application range of the display device is widened.
- the thermal expansion coefficient of the first polyimide layer is larger than that of the support and is preferably 5 to 30 ppm / K, more preferably 5 to 15 ppm / K.
- the thermal expansion coefficient is less than 5 ppm / K, the first polyimide layer itself becomes brittle and may be easily peeled off from the glass.
- the thermal expansion coefficient is larger than 30 ppm / K, the warp suppressing effect is weakened.
- the elastic modulus of the first polyimide layer is preferably 3 to 11 GPa, and preferably 5 to 10 GPa.
- the means for obtaining the first polyimide layer is not particularly limited, and one of them is to form the polyimide layer having a structural unit represented by the following general formula (1).
- it is a polyimide containing 50 mol% or more of a structural unit represented by the following general formula (1).
- X in the general formula (1) is an aromatic group or an alicyclic group, which is a tetravalent organic group having one or more aromatic rings or alicyclic rings, and R is 1 to 6 carbon atoms. Is a substituent.
- suitable specific examples of raw materials for forming the group X include, for example, pyromellitic dianhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA).
- R include, for example, —CH 3 , —CF 3 and the like.
- R is —CF 3
- the peelability at the interface between the first polyimide layer and the second polyimide layer can be improved, and separation of these can be facilitated.
- a general acid anhydride and diamine were used.
- Examples include structural units. Among them, pyromellitic dianhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA), 3,3 ′, 4,4 are preferably used.
- BPDA '-Biphenyltetracarboxylic dianhydride
- cyclohexanetetracarboxylic dianhydride cyclohexanetetracarboxylic dianhydride
- phenylenebis trimellitic monoester anhydride
- 4,4'-oxydiphthalic dianhydride benzophenone-3,4, 3 ', 4'-tetracarboxylic dianhydride, diphenylsulfone-3,4,3', 4'-tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4 4,4 '-(2,2'-hexafluoroisopropylidene) diphthalic dianhydride.
- diamines include m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 4,4'-diamino.
- a second polyimide layer having a thermal expansion coefficient equal to or higher than that of the first polyimide layer is laminated on the first polyimide layer.
- the thermal expansion coefficient of the second polyimide layer is preferably 10 to 80 ppm / K, and preferably 10 to 70 ppm / K. If the thermal expansion coefficient is less than 10 ppm / K, the second polyimide layer alone is too hard and easily cut, and workability may be deteriorated. On the other hand, if it exceeds 80 ppm / K, the effect of suppressing warpage is reduced. There is a risk of warping. Further, from the viewpoint of more effectively suppressing the warpage when the laminate is formed, the elastic modulus of the second polyimide layer is preferably 3 to 5 GPa.
- the thermal expansion coefficient of polyimide is reduced, transparency is lowered and retardation in the thickness direction (a phase difference due to a difference in birefringence) is increased.
- the second polyimide layer separated from the first polyimide layer is not suitable for use as, for example, a resin base material of a display device, a gas barrier film, or a touch panel substrate.
- the use of the second polyimide layer having a relatively large thermal expansion coefficient is allowed. This is because warpage as a laminate is suppressed by the presence of the first polyimide layer described above.
- the polyimide forming the second polyimide layer can be appropriately selected according to the use of the polyimide laminate.
- a display device such as a liquid crystal display device, an organic EL display device, electronic paper, a color filter, or a touch panel
- the polyimide which has a structural unit is mentioned, Preferably, it is a polyimide which contains 50 mol% or more of structural units represented by this General formula (2).
- this general formula (2) is a polyimide which contains 50 mol% or more of structural units represented by this General formula (2).
- it should have transparency, and the general formula The thing similar to what was demonstrated by (1) is mentioned.
- Preferred acid anhydrides include pyromellitic dianhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA), 3,3 ′, 4,4′- Biphenyltetracarboxylic dianhydride (BPDA), cyclohexanetetracarboxylic dianhydride, phenylenebis (trimellitic monoester anhydride), 4,4'-oxydiphthalic dianhydride, benzophenone-3,4,3 ' , 4'-tetracarboxylic dianhydride, diphenylsulfone-3,4,3 ', 4'-tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4 '-(2,2'-Hexafluoroisopropylidene) diphthalic dianhydride, 1,4-cyclohexanedicarboxylic acid, 1,2,3,
- diamines include m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 4,4'-diamino.
- Y is an aromatic or alicyclic tetravalent organic group.
- Y in the general formula (2) is preferably any one represented by the following formula (3).
- the second polyimide layer is formed of polyimide represented by the following formula (4).
- polyamic acid a polyimide precursor
- the resin solution of the polyamic acid substantially comprises a raw material diamine and an acid dianhydride.
- the weight average molecular weight (Mw) of the polyamic acid is preferably about 10,000 to 300,000 from the viewpoint of uniform film thickness during coating and the mechanical strength of the resulting polyimide.
- the preferred molecular weight range of the first and second polyimide layers is also the same molecular weight range as the polyamic acid.
- the first and second polyimide layers in the present invention are preferably obtained by a so-called casting method in which a polyimide or polyimide precursor resin solution is applied, dried, and heat-treated. . That is, in obtaining the polyimide laminate of the present invention, a polyimide or polyimide precursor resin solution is preferably applied to a support having a thermal expansion coefficient of 1 to 10 ppm / K, dried, heat-treated, and heated. After the first polyimide layer having an expansion coefficient of 5 to 30 ppm / K is formed, a polyimide or polyimide precursor resin solution is applied and dried, followed by heat treatment to form a second polyimide having a thermal expansion coefficient of 10 to 80 ppm / K. A polyimide layer is formed.
- the polyimide laminate thus obtained can be separated at the interface between the first polyimide layer and the second polyimide layer.
- at least one of the first and second polyimide layers be formed of a fluorine-containing polyimide having a fluorine atom in the polyimide structure.
- the peel strength between the first polyimide layer and the second polyimide layer can be preferably 1 to 200 N / m, and more preferably 1 to 100 N / m. Therefore, for example, it has a separability enough to be easily peeled off by human hands.
- the support has a thickness of 0.01 to 1.0 mm, preferably 0.02 to 0.7 mm, and the first polyimide layer has a thickness of 1 to 50 ⁇ m, The thickness is preferably 5 to 30 ⁇ m, and the thickness of the second polyimide layer is 5 to 30 ⁇ m, preferably 10 to 20 ⁇ m.
- the thickness of each of these layers also affects the warp generated in the laminate, so it is preferable to be within the above range.
- the polyimide laminate can be optimized by calculating the warpage deformation (warpage amount) based on the following idea for a laminate in which different materials are laminated. .
- the polyimide laminate of the present invention can be suitably used for obtaining a display device having a display unit on a resin substrate made of the second polyimide layer. That is, after a predetermined display portion is formed on the second polyimide layer in the polyimide laminate, separation may be performed at the interface between the first polyimide layer and the second polyimide layer.
- the support serves as a pedestal when the display unit is formed on the second polyimide layer side.
- the handleability of the resin base material (second polyimide layer) Even if dimensional stability or the like is ensured, the display device is not configured by being finally removed.
- the first polyimide layer is not finally removed to constitute a display device, and may be inferior in transparency.
- a predetermined display portion can be accurately and reliably formed on the second polyimide layer, and a thin, light, and flexible display device can be obtained.
- the polyimide laminate of the present invention can be applied to a substrate for a vapor deposition mask and a fan-out wafer level package (FOWLP) in addition to the display device.
- FOWLP fan-out wafer level package
- the display unit constituting the display device typically, an organic EL element including a TFT, an electrode, a light emitting layer, or the like corresponds to the display unit.
- a TFT In the case of a liquid crystal display device, a TFT, a drive circuit, and a color filter as necessary.
- the formation of TFT generally requires an annealing step of about 400 ° C., but the polyimide laminate in the present invention has heat resistance that can withstand such an annealing step.
- Light transmittance (%) The light transmittance at 500 nm was determined for a polyimide film (50 mm ⁇ 50 mm) with a U4000 spectrophotometer.
- CTE Coefficient of thermal expansion
- Thickness direction retardation Retardation in the thickness direction of the second polyimide layer (thickness direction retardation: Rth) was determined using an apparatus M-2000V manufactured by J. Woollam Japan.
- Synthesis example 1 While stirring in a 100 ml separable flask under a nitrogen stream, 8.49 g of TFMB was dissolved in GBL of 85 g of solvent. Subsequently, PMDA: 5.04g was added to this solution. Ten minutes later, 1.47 g of acid anhydride 6FDA was added. The molar ratio of acid anhydride to diamine was 0.998. Thereafter, the solution was stirred at room temperature for 4 hours to conduct a polymerization reaction, and kept for a whole day and night. A viscous colorless polyamic acid solution was obtained, and it was confirmed that polyamic acid A having a high degree of polymerization was produced.
- Synthesis Examples 2-7 A polyamic acid solution was prepared in the same manner as in Synthesis Example 1 except that the acid anhydride and diamine were changed to the mass composition shown in Table 1, and polyamic acids (resins) B to G were obtained.
- Example 1 After adding the solvent GBL to the polyamic acid solution A obtained in Synthesis Example 1 above and diluting so that the viscosity becomes 3000 cP, the size is 150 mm ⁇ 150 mm, the thickness is 0.7 mm, and the CTE is 3.5 ppm / It apply
- polyimide A polyimide A
- the polyamic acid solution B obtained in Synthesis Example 2 is diluted with DMAc (solvent) so that the viscosity becomes 3000 cP, and the film thickness after the heat treatment becomes about 10 ⁇ m. It was applied to. Subsequently, heat treatment was performed at 90 ° C. for 3 minutes and then at 110 ° C. for 10 minutes, and preliminary drying was performed. And it heated up from 90 degreeC to 360 degreeC over 30 minutes, the 2nd polyimide layer (polyimide B) of 150 mm x 150 mm was formed, and the polyimide laminated body concerning Example 1 was obtained.
- DMAc solvent
- each thermal expansion coefficient (CTE), light transmittance, elastic modulus, glass transition temperature (Tg) ) And retardation are separately applied separately to the same glass substrate as described above so that the polyamic acid solution obtained in Synthesis Examples 1 and 2 is about 15 ⁇ m after heat treatment.
- Heat treatment is performed at 90 ° C. for 3 minutes and then 110 ° C. for 10 minutes, and after preliminary drying, the temperature is raised from 90 ° C. to 360 ° C.
- Example 2 As shown in Table 2, resin C obtained in Synthesis Example 3 was used as the first polyimide layer, and resin B obtained in Synthesis Example 2 was used as the second polyimide layer.
- a polyimide laminate was obtained by the procedure (a polyimide laminate comprising “glass / resin C / resin B” shown in “laminate configuration” in Tables 2 and 3; the same applies to the following examples and comparative examples. (In this order, “support / first polyimide layer / second polyimide layer”). The physical properties such as warpage were also measured for this polyimide laminate. The results are also shown in Tables 2 and 3.
- Example 3 As shown in Table 2, the resin G obtained in Synthesis Example 7 is used as the first polyimide layer, and the resin B obtained in Synthesis Example 2 is used as the second polyimide layer. A polyimide laminate was obtained by the procedure. The polyimide laminate was also measured for physical properties such as warpage, and was subjected to simulation evaluation of warpage. The results are also shown in Tables 2 and 3.
- Comparative Examples 1 to 3 A polyimide laminate was prepared by the same procedure as in Example 1 except that a three-layer structure using the polyimide resin shown in Table 2 was used, and physical properties such as warpage were measured. In addition, the amount of warpage (curl) was compared with the calculated value by simulation.
- Comparative Example 4 After adding DMAc to the polyamic acid solution B obtained in Synthesis Example 2 and diluting it to have a viscosity of 3000 cP, the film thickness after heat treatment using the spin coater on the same glass substrate as in Example 1 is It apply
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Abstract
Description
(1)熱膨張係数が1~10ppm/Kの支持体上に、第1のポリイミド層と、第2のポリイミド層の順に複数のポリイミド層を備える積層体であって、
第1のポリイミド層の膜厚が1~50μmであり、熱膨張係数が支持体の熱膨張係数以上、5~30ppm/kであり、ガラス転移温度が300℃以上であること、
第2のポリイミド層の膜厚が5~30μmであり、熱膨張係数が第1のポリイミド層の熱膨張係数以上であること、及び
第1のポリイミド層と第2のポリイミド層は、その界面で剥離可能であることを特徴とするポリイミド積層体。
(3)第1のポリイミド層の弾性率が3~11GPaであり、第2のポリイミド層の弾性率が3~5GPaである上記(1)又は(2)のポリイミド積層体。
(4)第2のポリイミド層の熱膨張係数が10~80ppm/Kである上記(1)~(3)のいずれかのポリイミド積層体。
(5)第1のポリイミド層と第2のポリイミド層との剥離強度が、1~100N/mである上記(1)~(4)のいずれかのポリイミド積層体。
(6)第1のポリイミド層が、下記一般式(1)で表される構造単位を有するポリイミドを含有する上記(1)~(5)のいずれかのポリイミド積層体。
(7)第2のポリイミド層が、下記一般式(2)で表される構造単位を有するポリイミドを含む上記(1)~(6)のいずれかのポリイミド積層体。
(8)第2のポリイミド層が、波長500nmにおける光透過率が80%以上であり、かつ、厚さ方向のリタデーションが200nm以下である上記(1)~(7)のいずれかのポリイミド積層体。
(9)第2のポリイミド層上に所定の表示部を形成した後、第1のポリイミド層と第2のポリイミド層との界面で分離して、第2のポリイミド層からなる樹脂基材上に表示部を備えた表示装置を得るのに用いられる上記(1)~(8)のいずれかのポリイミド積層体。
・PMDA:ピロメリット酸二無水物
・BPDA:3,3',4,4'-ビフェニルテトラカルボン酸二無水物
・6FDA:2,2'-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物
・AAPBZ:5-アミノ-2-(4-アミノフェニル)ベンゾイミダゾール
・BAPP:2,2'-ビス(4-アミノフェノキシフェニル)プロパン
・TFMB:2,2'-ビス(トリフルオロメチル)-4,4'-ジアミノビフェニル
・DMAc:N,N-ジメチルアセトアミド
・GBL:γブチルラクトン
ポリイミドフィルム(50mm×50mm)をU4000形分光光度計にて、500nmにおける光透過率を求めた。
3mm×15mmのサイズのポリイミドフィルムを、熱機械分析(TMA)装置にて5.0gの荷重を加えながら一定の昇温速度(10℃/min)で30℃から280℃の温度範囲で引張り試験を行い、250℃から100℃までの降温時における温度に対するポリイミドフィルムの伸び量から熱膨張係数(ppm/K)を測定した。
テンションテスターを用い、幅12.4mm、長さ160mmのポリイミドフィルムを10kgの荷重を加えながら50mm/minで引っ張り試験を行い、25℃における引張り弾性率(E’)を求めた。
ガラス基板に第1のポリイミド層、第2のポリイミド層を形成した後、100cm四方の積層体を作製した。そして、第2層目のポリイミド層面を上にして、23℃、50%RHで、24時間静置した。静置後、積層体の反りを1mm厚のスペーサで判定した。即ち、スペーサが積層体の下側に入るものは反りあり「×」とし、スペーサが積層体の下側にシートが入らないものは反りなし「○」とした。
計算方法としては熱変形と自重が釣り合った状態の最終的な反り変形について積層シェル要素を用いて離散化し数値計算的にコンピューターで演算を実施する有限要素法を用いた(図2参照)。
数値が大きいほど、カール(反り)を生じ易いことを示す。
ジェーエ・ウーラム・ジャパン製装置M-2000Vを用いて、第2のポリイミド層の厚さ方向のリタデーション(厚さ方向位相差:Rth)を求めた。
ガラスに樹脂を塗工して得られた積層体を、目視・手作業にて品質評価を行った。ガラス基板から剥離したり、フィルムが脆くて切れて評価できなかったり場合は「×」とし、特に外観上問題なかった場合は「○」とした。
ポリイミド積層体の第2のポリイミド層の表面に対し垂直にカッターナイフで第1のポリイミド層を貫通してガラス基板表面に達するように、ポリイミド積層体の各辺の端部から略5mmの距離を開けて各辺と並行な直線の切り口を4カ所付けたのち、切り口によって区切られた剥離範囲について、第1のポリイミド層と支持体との間を手で剥離した(図1)。次いで、第1のポリイミド層と第2のポリイミド層の界面を同様にして手で剥離した。手で剥離可能なら「○」とし、剥離できない場合は「×」とした。また、剥離強度を表3にまとめて示す。
窒素気流下で、100mlのセパラブルフラスコの中で攪拌しながら、TFMB:8.49gを溶剤85gのGBLに溶解させた。次いで、この溶液にPMDA:5.04gを加えた。10分後、酸無水物6FDA:1.47gを加えた。酸無水物とジアミンのモル比を0.998とした。その後、溶液を室温で4時間攪拌を続けて重合反応を行い、一昼夜保持した。そして、粘稠な無色のポリアミド酸溶液が得られて、高重合度のポリアミド酸Aが生成されていることが確認された。
酸無水物及びジアミンを表1に示す質量組成に変更した以外は合成例1と同様にしてポリアミド酸溶液を調製し、ポリアミド酸(樹脂)B~Gを得た。
上記合成例1で得られたポリアミド酸溶液Aに、溶剤GBLを加えて、粘度が3000cPになるように希釈した上で、サイズが150mm×150mm、厚みが0.7mm、CTEが3.5ppm/Kのガラス基板上に、スピンコーターを用いて製膜後の厚みが14μmになるように塗布した。続いて、90℃×3分間、それから110℃×10分間の熱処理を行い、予備乾燥を実施した。そして、30分をかけて90℃から360℃まで昇温させ、ガラス基板上に150mm×150mmの第1のポリイミド層(ポリイミドA)を形成した。
また、反り量(カール)については、シミュレーション計算も行い、その結果も表2に示す。シミュレーションの結果は実測による反り判定結果と整合していた。
表2に示すように、合成例3で得られた樹脂Cを第1のポリイミド層とし、合成例2で得られた樹脂Bを第2のポリイミド層とすること以外、実施例1と同様な手順によってポリイミド積層体を得た(表2及び3の「積層体構成」に示した「ガラス/樹脂C/樹脂B」からなるポリイミド積層体であり、以下の実施例、比較例についても同様にこの順「支持体/第1のポリイミド層/第2のポリイミド層」で示す。)。このポリイミド積層体についても、反りなどの物性を測定した。その結果も表2及び表3に示す。
表2に示すように、合成例7で得られた樹脂Gを第1のポリイミド層とし、合成例2で得られた樹脂Bを第2のポリイミド層とすること以外、実施例1と同様な手順によってポリイミド積層体を得た。このポリイミド積層体についても、反りなどの物性を測定した、併せて反り量のシミュレーション評価を行った。それらの結果も表2及び表3に示す。
表2に示したポリイミド樹脂を用いた三層構成とすること以外、実施例1と同様の手順によってポリイミド積層体を作成し、反り等の物性を測定した。併せて、反り(カール)量については、シミュレーションによる計算値と対比を行った。
合成例2で得られたポリアミド酸溶液Bに、DMAcを加えて、粘度が3000cPになるように希釈した上で、実施例1と同じガラス基板上にスピンコーターを用いて熱処理後の膜厚が約15μmとなるように塗布した。そして、30分をかけて90℃から360℃まで昇温させ、ガラス基板上に100mm×100mmのポリイミド層を形成して、二層構成のポリイミド積層体を得た。
2 第1のポリイミド層
3 第2のポリイミド層
Claims (10)
- 熱膨張係数が1~10ppm/Kの支持体上に、第1のポリイミド層と、第2のポリイミド層の順に複数のポリイミド層を備える積層体であって、
第1のポリイミド層の膜厚が1~50μmであり、熱膨張係数が支持体の熱膨張係数以上、5~30ppm/kであり、ガラス転移温度が300℃以上であること、
第2のポリイミド層の膜厚が5~30μmであり、熱膨張係数が第1のポリイミド層の熱膨張係数以上であること、及び
第1のポリイミド層と第2のポリイミド層は、その界面で剥離可能であることを特徴とするポリイミド積層体。 - 第2のポリイミド層は波長500nmにおける光透過率が80%以上である請求項1に記載のポリイミド積層体。
- 第1のポリイミド層の弾性率が3~11GPaであり、第2のポリイミド層の弾性率が3~5GPaである請求項1又は2に記載のポリイミド積層体。
- 第2のポリイミド層の熱膨張係数が10~80ppm/Kである請求項1~3のいずれかに記載のポリイミド積層体。
- 第1のポリイミド層と第2のポリイミド層との剥離強度が、1~100N/mである請求項1~4のいずれかに記載のポリイミド積層体。
- 第2のポリイミド層が、波長500nmにおける光透過率が80%以上であり、かつ、厚さ方向のリタデーションが200nm以下である請求項1~7のいずれかに記載のポリイミド積層体。
- 第2のポリイミド層上に所定の表示部を形成した後、第1のポリイミド層と第2のポリイミド層との界面で分離して、第2のポリイミド層からなる樹脂基材上に表示部を備えた表示装置を得るのに用いられる請求項1~8のいずれかに記載のポリイミド積層体。
- 熱膨張係数が1~10ppm/Kの支持体上に、ポリイミド又はポリイミド前駆体の樹脂溶液を塗布・乾燥し、加熱処理して熱膨張係数が支持体の熱膨張係数以上、5~30ppm/Kの第1のポリイミド層を形成した後、前記樹脂溶液とは異なるポリイミド又はポリイミド前駆体の樹脂溶液を塗布・乾燥し、加熱処理して熱膨張係数が第1のポリイミド層の熱膨張係数以上の第2のポリイミド層を形成することを特徴とするポリイミド積層体の製造方法。
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