WO2018221374A1 - ポリイミドフィルムと無機基板の積層体 - Google Patents
ポリイミドフィルムと無機基板の積層体 Download PDFInfo
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- WO2018221374A1 WO2018221374A1 PCT/JP2018/020016 JP2018020016W WO2018221374A1 WO 2018221374 A1 WO2018221374 A1 WO 2018221374A1 JP 2018020016 W JP2018020016 W JP 2018020016W WO 2018221374 A1 WO2018221374 A1 WO 2018221374A1
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- polyimide film
- inorganic substrate
- film
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- polyimide
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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Definitions
- a laminate of a polyimide film and an inorganic substrate such as glass more specifically, by laminating a polyimide film on an inorganic substrate, a flexible polyimide film is temporarily supported, and a functional element such as an electronic device is placed on the polyimide film. It is related with the laminated body of the polyimide film and inorganic substrate which are used in order to manufacture the flexible functional element which uses a polyimide film as a board
- the functional element When forming the functional element on the surface of the polymer film, it is ideal to process by a so-called roll-to-roll process utilizing the flexibility that is a characteristic of the polymer film.
- a process technology for a rigid flat substrate such as a wafer base or a glass substrate base has been constructed so far. Therefore, in order to form a functional element on a polymer film using existing infrastructure, the polymer film is bonded to a rigid support made of an inorganic material such as a glass plate, a ceramic plate, a silicon wafer, or a metal plate.
- a process is used in which a desired element is formed thereon and then peeled off from the support.
- the polymer film or polymer precursor solution is coated on the inorganic substrate and dried and cured on the support to form a film because the heat-resistant adhesive means for attaching the polymer film to the inorganic substrate is poor.
- Techniques used for such applications are known.
- a technique for forming a plurality of layers and using a part as a sacrificial layer, or a technique for functionally separating an adhesive / peeling function and a film physical property has been proposed (patent) References 1-3). Since the polymer film obtained by such means is brittle and easily torn, the functional element formed on the surface of the polymer film often breaks when peeled from the support.
- JP 2016-120629 A Japanese Unexamined Patent Publication No. 2016-120630 Japanese Patent No. 4834758 JP 2010-283262 A JP 2011-11455 A
- This type of defect is a blister defect (sometimes referred to simply as a blister, or a bubble, uki or bubble).
- a blister defect sometimes referred to simply as a blister, or a bubble, uki or bubble.
- the present inventors were able to reduce blisters by cleaning (washing) the polymer film and the glass plate (inorganic substrate) surface before bonding. However, even if washing was performed carefully, the generation of blisters was not eradicated.
- the present inventors have found that in a laminate of a polymer film and a support made of an inorganic material, the adhesive layer is thin, or the adhesive layer is substantially absent.
- the inventors have found a formulation that can suppress the generation of blisters and can achieve a high production yield, and have reached the present invention.
- the present invention has the following configuration.
- a laminate of a polyimide film and an inorganic substrate wherein the laminate of the polyimide film and the inorganic substrate satisfies at least the condition (a) or (b).
- the number density of blister defects is 50 pieces / square meter or less, the average height of blisters is 2 ⁇ m or less, and the product of the blister number density (pieces / square meter) and the average height of blisters ( ⁇ m) is 20 or less.
- the number of blisters having a height of 3 ⁇ m or more is 10 pieces / square m.
- the foreign matter is an inorganic or organic substance present in the environment, and adheres to the film or the inorganic substrate due to static electricity or the like.
- inorganic substances can be removed relatively easily by washing or the like.
- Substances that are characteristic in the type of organic foreign matter adhering to the surface of the polyimide film are polyimide particles. It is presumed that such polyimide particles are generated in a polyimide film manufacturing process or a slitting process. Foreign substances resulting from such polyimide can be removed relatively easily by washing, as with inorganic substances.
- the present invention reduces the height of the blister even when organic foreign matter exists between the film and the inorganic substrate by performing heat treatment under a predetermined condition after bonding the film and the inorganic substrate, and there is a practical problem.
- the feature is that it has been improved to a level that does not. That is, the effect of the present invention is that the blister height is low when the foreign matter inside is a carbide, even if it is a blister having foreign matter inside, and a decrease in yield can be minimized.
- the organic foreign substance-containing blister having a problematic height can be converted into a carbide foreign substance-containing blister by a specific processing method, and the blister height can be reduced to a level that does not cause a problem.
- the effect of the present invention can be made more remarkable by controlling the cooling rate after the heat treatment in a predetermined range. That is, by cooling at a specific speed, the blister swollen with the decomposition gas of the organic substance can be quickly contracted. If the cooling rate is unnecessarily long, the elasticity of the polyimide film, which had been reduced at a high temperature, returns to the original value before the blister sufficiently shrinks, and the shape retention of the polyimide film itself increases, so the blister In some cases, it becomes impossible to sufficiently reduce the height. Large substrates tend to have spots on the heating and cooling rates. In the present invention, it is particularly important to reduce the spots of the cooling rate. Therefore, in the present invention, it is preferable to cool the laminated body by bringing it into direct contact with a high specific heat substance such as a metal plate during cooling.
- a high specific heat substance such as a metal plate during cooling.
- a sufficient effect can be obtained by washing the polyimide film before lamination with ultrapure water that has been subjected to ozone treatment in advance. That is, blisters are caused by decomposed gas generated from organic foreign matters.
- ozone treatment By cleaning the polyimide surface with ultrapure water that decomposes and removes organic matter in advance by ozone treatment, organic foreign matter that may have originally adhered can be cleaned and removed. Since it decomposes
- the ozone treatment can be performed, for example, by aeration of cleaning water into ozone-containing clean air generated by an ozonizer or the like.
- the ozone concentration in the wash water is preferably 3 ppm or more, preferably 6 ppm or more, more preferably 9 ppm or more, and even more preferably 20 ppm or more.
- the upper limit of the ozone concentration is not particularly limited, but is about 200 ppm.
- FIG. 1 is a schematic explanatory view of blisters in a laminate of a polyimide film and an inorganic substrate of the present invention.
- an inorganic substrate is used as the support substrate.
- the inorganic substrate is a plate-like material made of an inorganic material, and examples thereof include a glass plate, a ceramic plate, a semiconductor wafer, and a metal plate.
- a composite substrate in which two or more selected from a glass plate, a ceramic plate, a semiconductor wafer, and a metal plate are laminated can also be used.
- a composite in which one or more materials selected from glass, ceramic, and metal are dispersed in powder form in other inorganic or organic materials can be exemplified.
- Further examples include a substrate material having a fiber-reinforced composite structure in which one or more kinds of fibrous materials selected from glass, ceramic, and metal are combined in another inorganic material or an organic material.
- quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (non-alkali), borosilicate glass (microsheet), aluminosilicate glass and the like can be exemplified.
- Examples of the ceramic plate which is an inorganic substrate in the present invention include alumina, mullite, aluminum nitride, silicon carbide, silicon nitride, boron nitride, crystallized glass, cordurite, lithiarite, Pb-BSG + CaZrO3 + Al2O3, crystallized glass + Al2O3.
- metal material constituting the metal plate in the present invention single element metals such as W, Mo, Pt, Fe, Ni, Au, Inconel, Monel, Nimonic, carbon copper, Fe-Ni-based Invar alloy, Super Invar alloy, Such alloys are included.
- a multilayer metal plate formed by adding other metal layers and ceramic layers to these metals is also included. In this case, if the total CTE with the additional layer is low, Cu, Al or the like is also used for the main metal layer.
- the metal used as the additional metal layer is limited as long as it has strong adhesion to the polyimide film, no diffusion, and good chemical resistance and heat resistance. Although it is not, chromium, nickel, TiN, and Mo containing Cu are mentioned as a suitable example.
- a silicon wafer, a silicon carbide wafer, a compound semiconductor wafer, or the like can be used as the semiconductor wafer in the present invention.
- the silicon wafer is obtained by processing single crystal or polycrystalline silicon on a thin plate, and is an n-type.
- all of silicon wafers and intrinsic silicon wafers doped in p-type are included, and silicon wafers in which a silicon oxide layer and various thin films are deposited on the surface of the silicon wafer are also included.
- Wafer can be used such as a compound semiconductor wafer.
- the area of the inorganic substrate in the present invention is preferably 0.157 square meters or more. More specifically, it is preferably a rectangle having a long side of 45 cm or more and a short side of 35 cm or more.
- These support inorganic substrates are subjected to activation treatment such as UV ozone treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, flame treatment, itro treatment, UV ozone treatment, and exposure treatment to active gas. Can do. These treatments mainly have the effect of improving the adhesion to the polyimide film by activating the surface of the inorganic substrate as well as the cleaning effect of removing adhered contaminants such as organic substances on the surface of the inorganic substrate.
- the polyimide in the present invention is a multimer by an imide bond.
- polyimide is obtained as a condensate of tetracarboxylic dianhydride and diamine.
- a polyamic acid (polyimide precursor) solution obtained by reacting tetracarboxylic dianhydride and diamine in a solvent is applied to a support and dried to form a precursor film.
- a method is known in which an imidization reaction is caused by heating or the action of a catalyst to convert it into polyimide.
- a method of peeling off the precursor film from the support and imidizing is common.
- an aromatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride can be preferably used.
- An aromatic tetracarboxylic dianhydride is preferable from the viewpoint of heat resistance, and an alicyclic tetracarboxylic dianhydride is preferable from the viewpoint of light transmittance.
- Tetracarboxylic dianhydride may be used alone or in combination of two or more.
- aromatic tetracarboxylic acid in the present invention, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) ) Phenyl] propanoic anhydride and the like.
- Examples of the alicyclic tetracarboxylic acids in the present invention include fats such as cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3 ′, 4,4′-bicyclohexyltetracarboxylic acid.
- Examples include cyclic tetracarboxylic acids and acid anhydrides thereof.
- dianhydrides having two anhydride structures are preferred.
- alicyclic tetracarboxylic acids may be used independently and may use 2 or more types together.
- the alicyclic tetracarboxylic acids are, for example, preferably 80% by mass or more of all tetracarboxylic acids, more preferably 90% by mass or more, and further preferably 95% by mass or more.
- the diamines in the present invention are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like that are usually used for polyimide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferred, and among the aromatic diamines, aromatic diamines having a benzoxazole structure can be used. When aromatic diamines having a benzoxazole structure are used, it is possible to develop a high elastic modulus, a low heat shrinkage, and a low linear expansion coefficient as well as high heat resistance. Diamines may be used alone or in combination of two or more.
- aromatic diamines examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl) -2-propyl.
- Benzene bisaniline
- 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl
- 4,4'-bis (3-aminophenoxy) biphenyl bis [4- (3-aminophenoxy) phenyl] ketone
- bis [4- (3-aminophenoxy) phenyl] sulfide bis [ 4- (3-aminophenoxy) phenyl] sulfone
- 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis 4- (3-aminophenoxy)
- Examples of the aliphatic diamines in the present invention include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, and the like.
- Examples of the alicyclic diamines in the present invention include 1,4-diaminocyclohexane, 4,4′-methylenebis (2,6-dimethylcyclohexylamine) and the like.
- Examples of the diamine having a benzoxazole structure in the present invention include 5-amino-2- (p-aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, and 5-amino-2.
- the polyimide preferably used is preferably a film composed of a condensate of an aromatic tetracarboxylic dianhydride and an aromatic diamine, (A) a film of a condensation product of an aromatic tetracarboxylic dianhydride and a diamine containing a diamine having at least a benzoxazole skeleton, (B) a film of a condensation product of an aromatic tetracarboxylic dianhydride and a diamine containing a diamine having an ether bond in the molecule, (C) a film of a condensate of an aromatic tetracarboxylic dianhydride and a diamine containing at least phenylenediamine, (D) a film of a condensate of biphenyltetracarboxylic dianhydride and an aromatic diamine, It is preferable that it consists of at least 1 type of polyimide film selected from these.
- the film thickness of the polyimide film in the present invention is not particularly limited, but is preferably 0.5 ⁇ m to 200 ⁇ m, and more preferably 3 ⁇ m to 50 ⁇ m. If the thickness is 0.5 ⁇ m or less, it is difficult to control the film thickness, and there is a possibility that a part of the polyimide is lost. On the other hand, when the thickness is 200 ⁇ m or more, production takes time, and it may be difficult to control film thickness unevenness.
- the film thickness unevenness of the polyimide film is essential to be 5% or less, more preferably 4% or less, and still more preferably 3% or less.
- the film of the condensate of tetracarboxylic dianhydride and diamine of the present invention can be obtained by a solution film forming method.
- the polyimide film-forming method uses a stainless steel roll or an endless belt, or a polymer film such as PET as a long or endless support, and a polyimide resin precursor solution is applied on the support, After drying, the film is peeled off from the support to form a polyimide precursor film.
- both ends of the film are held with clips or pins and conveyed, and heat treatment is further applied to chemically react the polyimide precursor to polyimide. This is a method for obtaining a film.
- the polyimide film obtained using such a technique has a film thickness unevenness of 5% or less, preferably 3.6% or less, more preferably 2.4% or less, and a tensile breaking strength of 90 MPa or more, preferably 180 MPa or more, More preferably, it becomes a polyimide film of 350 MPa or more, more preferably 450 MPa or more.
- the silicon oxide component contained in the polyimide film is preferably 6000 ppm or less, preferably 4500 ppm or less, more preferably 1800 ppm or less, and still more preferably 900 ppm or less. Addition of an excessive lubricant may increase the roughness of the film surface and inhibit the peelability of the second polyimide film.
- a known adhesive or pressure sensitive adhesive such as a silicone resin, an epoxy resin, an acrylic resin, or a polyester resin can be used as an adhesive means between the inorganic substrate as a support and the polyimide film.
- a preferable bonding means in the present invention is an extremely thin, adhesive / adhesive layer bonding means having a film thickness of 5 ⁇ m or less, or preferably an adhesive means substantially using no adhesive or pressure-sensitive adhesive.
- the area of the laminate of the polyimide film and inorganic substrate in the present invention is preferably 0.157 square meters or more.
- the area of the laminate of the polyimide film and the inorganic substrate refers to the area of the overlapping portion.
- the area of the laminate of the polyimide film and the inorganic substrate is preferably 0.25 square meters or more, more preferably 0.46 square meters or more, still more preferably 0.62 square meters or more, still more preferably 0.00. More than 98 square meters.
- a method of adhering using a silane coupling agent can be used as an adhering means which does not substantially use an adhesive or an adhesive. That is, in this invention, it is preferable to have a silane coupling agent layer between an inorganic substrate and a polyimide film.
- the silane coupling agent in the present invention refers to a compound that is physically or chemically interposed between an inorganic plate and a polyimide film and has an action of increasing the adhesive force between the two.
- silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, Vinyltrimethoxysilane,
- silane coupling agent examples include n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, Ethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane , N-octyltriethoxys
- alkoxysilanes such as tetramethoxysilane and tetraethoxysilane may be appropriately added to the silane coupling agent.
- other alkoxylanes such as tetramethoxysilane, tetraethoxysilane, etc. are added to the silane coupling agent as appropriate or not, mixing and heating operations are added to slightly react. It may be used after it has been advanced.
- the silane coupling agent preferably used in the present invention is preferably a silane coupling agent having a chemical structure having one silicon atom per molecule of the coupling agent.
- particularly preferred silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysi
- the coating method of the silane coupling agent in the present invention is not particularly limited, and a general wet coating method or a coating method in a gas phase can be used.
- a general wet coating method or a coating method in a gas phase can be used.
- spin coating, capillary coating, bar coating, applicator, die coating, comma coating, screen printing, gravure printing, inkjet printing are performed using a silane coupling agent stock solution or solvent solution, preferably an alcohol solution.
- Techniques such as spray coating and spray coating can be used.
- a gas phase coating method preferably via a gas phase can be used.
- the vapor phase coating method coating is performed by exposing an inorganic substrate to a vaporized silane coupling agent.
- the silane coupling agent application may be rephrased as a silane coupling agent treatment.
- Vaporization refers to a state in which a vapor of a silane coupling agent, that is, a substantially gaseous silane coupling agent or a particulate silane coupling agent is present. Exposure means that the organic polymer film is in contact with the vaporized or gas containing a silane coupling agent or in a vacuum state.
- the vapor of the silane coupling agent can be easily obtained by heating the liquid silane coupling agent to a temperature from 30 ° C. to the boiling point of the silane coupling agent.
- the above silane coupling agent is produced even if it is below the boiling point.
- a state in which fine particles of a silane coupling agent coexist can also be used.
- the boiling point of the silane coupling agent varies depending on the chemical structure, but is generally in the range of 100 to 250 ° C. However, heating at 200 ° C. or higher is not preferable because it may cause a side reaction on the organic group side of the silane coupling agent.
- the thickness of the silane coupling agent layer in the present invention is preferably 5 nm or more, preferably 9 nm or more, preferably 18 nm or more, and more preferably 45 nm or more.
- the upper limit of the film thickness of the silane coupling agent is preferably 500 nm or less, more preferably 390 nm or less, and still more preferably 240 nm or less.
- the film thickness of the silane coupling agent can be measured by electron microscope observation of the cross section of the laminate.
- the environment in which the silane coupling agent is heated may be under pressure, normal pressure, or reduced pressure. However, in order to promote vaporization of the silane coupling agent, it is generally preferably under normal pressure or reduced pressure. Since silane coupling agents are often classified as flammable liquids, it is preferable to perform a vaporization operation in an airtight container, preferably after replacing the inside of the container with an inert gas. On the other hand, from the viewpoint of improving production efficiency and reducing the cost of production equipment, it is desirable to apply a silane coupling agent in an environment that does not use vacuum.
- an organic polymer film in the chamber under normal pressure, fill the carrier gas at approximately normal pressure including the silane coupling agent vaporized in the chamber, deposit the silane coupling agent, and then vaporize again.
- the reaction can be carried out at substantially atmospheric pressure until the silane coupling agent is returned to the state without the silane coupling agent.
- UV ozone treatment On the side of the polyimide film that will be the polyimide film of the present invention to be bonded to at least the inorganic substrate, UV ozone treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, flame treatment, itro treatment, acid treatment, alkali treatment, activity
- An activation process such as a gas exposure process can be performed.
- These treatments mainly have the effect of improving the adhesion to the inorganic substrate by activating the polyimide film surface, as well as the cleaning effect of removing adhered contaminants such as organic substances on the polyimide film surface.
- a method for producing a polyimide / inorganic substrate phase laminate in which an inorganic substrate and a polyimide film are laminated via a silane coupling material the inorganic substrate coated with a silane coupling agent and the polyimide film are overlapped, or the inorganic substrate and It is preferable to superimpose polyimide films coated with a silane coupling agent and laminate them together under pressure. Further, both the inorganic substrate and the polyimide film may be treated with a silane coupling material.
- a pressurizing method a normal press performed while applying normal temperature or heat in the atmosphere, and a press in a vacuum can be given.
- a preferable pressure is 0.5 MPa to 20 MPa, more preferably 2 to 10 MPa.
- a preferred temperature range is 0 ° C. to 550 ° C., more preferably 10 ° C. to 300 ° C. If the temperature is too high, the film and the inorganic substrate may be deteriorated.
- the degree of vacuum is sufficient with a normal oil rotary pump, and about 10 Torr or less is sufficient.
- the adhesion can be stabilized by heat treatment.
- the heat treatment temperature at this time is preferably in the range of 50 ° C. to 550 ° C. More preferably, it is in the range of 100 ° C to 500 ° C.
- the adhesion stability can be improved by heat treatment. When the temperature is 50 ° C. or lower, the effect of improving the adhesion stability is small, and when it exceeds 550 ° C., thermal deterioration of the polyimide film tends to proceed.
- a method for producing a laminate of a polyimide film and an inorganic substrate a method of forming a polyimide film by heat treatment after pouring a solution obtained by dissolving the polyimide or polyimide precursor in an organic solvent on an inorganic substrate It can also be taken.
- the solvent only needs to be able to dissolve polyimide or a polyimide precursor, and an aprotic polar solvent can be preferably used.
- N, N-dilower alkylcarboxylamides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, 1,3-dimethyl-2-imidazolidinone, ⁇ -butyrolactone, diglyme, m-cresol, hexamethylphosphoramide, N-acetyl-2-pyrrolidone Hexamethylphosphoramide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, p-chlorophenol and the like.
- the solvent may be a mixture of two or more.
- the conditions for the heat treatment for imidizing the polyimide precursor are not particularly limited, but are at least 150 ° C. to 200 ° C., more preferably 160 ° C. to 190 ° C. for 10 minutes or more, preferably After the heat treatment for 30 minutes or more, particularly preferably for 60 minutes or more, the heat treatment may be performed at a maximum temperature of 400 ° C. to 550 ° C., preferably 430 ° C. to 530 ° C., more preferably 460 ° C. to 530 ° C. preferable.
- the time for heat treatment at a temperature of 200 ° C. or higher can be appropriately determined, and is not particularly limited.
- a solution in which the polyimide or polyimide precursor is dissolved in an organic solvent is applied onto an inorganic substrate, and in some cases, a part of the solution is dried, and a polyimide film is laminated thereon, followed by drying. is there.
- a solution in which the polyimide or polyimide precursor is dissolved in an organic solvent is applied onto an inorganic substrate, and in some cases, partially dried, and another type of polyimide or polyimide precursor is dissolved in an organic solvent. It is also possible to apply a known method such as applying the solution to the inorganic substrate and then drying it.
- the blister in the present invention refers to a defect in a laminate of a polyimide film and an inorganic substrate in which a gap is generated between the polyimide film and the inorganic substrate, and the polyimide film side swells in a tent shape or a dome shape.
- the blister of the present invention refers to a size that can be confirmed with the naked eye. More specifically, when the blister observed in the plane direction is a circle, the diameter is 50 ⁇ m or more. Here, the diameter is an average value of the major axis and the minor axis when the blister is distorted.
- the number of blisters having a height of 3 ⁇ m or more is preferably 10 or less per square meter, more preferably 7 or less, and 4 or less. More preferably, it is more preferably 2 or less. More preferably, it is zero.
- the number of blisters having a height of 2.2 ⁇ m or more is preferably 10 or less per square meter, more preferably 7 or less, even more preferably 4 or less, More preferably, it is 2 or less. More preferably, it is zero.
- the number of blisters having a height of 1.4 ⁇ m or more is preferably 10 or less per square meter, more preferably 7 or less, and even more preferably 4 or less, More preferably, it is 2 or less. More preferably, it is zero.
- the number of blisters having a height of 0.8 ⁇ m or more is preferably 10 or less per square meter, more preferably 7 or less, further preferably 4 or less, More preferably, it is 2 or less. More preferably, it is zero.
- the number density of the total number of blisters in the present invention is preferably 50 pieces / square meter or less.
- the height of the blister in the present invention can be measured with a 3D laser microscope.
- the average value of the heights of the blister defect portions is preferably 2 ⁇ m or less, more preferably 1.6 ⁇ m or less, still more preferably 1.2 ⁇ m or less, and 0.8 ⁇ m or less. Is even more preferred. If the average value of the heights of the blister defects exceeds this range, the production yield is significantly reduced.
- the product of the blister number density (pieces / square meter) and the average height ( ⁇ m) of the blisters is preferably 20 or less.
- the height of the blister is an important factor in determining the quality of the laminate of the present invention, but the average value of the blister height is calculated to be low when there are many blisters having a low height.
- the product of the average blister height and the blister number distribution it is possible to obtain a parameter that is effective for improving the yield of flexible device manufacturing.
- the blister in the present invention particularly handles a blister containing carbide particles (carbide foreign matter) in the voids.
- the carbide is black or black-brown, and is at least when the total of C element and O element exceeds 50% with respect to all elements in SEM-EDX, or exhibits a spectrum peculiar to carbide in microscopic IR analysis. A substance that satisfies any of the conditions.
- the color of foreign matter (particles) contained can be easily identified by observation from the glass plate side. In the case of an opaque inorganic substrate, the film side can be incised and observed.
- the laminate of the polyimide film and the inorganic substrate of the present invention can be obtained by performing a heat treatment at a temperature of 350 ° C. or more and less than 600 ° C. after the polyimide film and the inorganic substrate are laminated.
- the lower limit of the heat treatment temperature is preferably 370 ° C. or higher, preferably 390 ° C. or higher, and preferably 420 ° C. or higher.
- the upper limit of the heat treatment temperature is preferably 560 ° C. or less, more preferably 520 ° C. or less, preferably 490 ° C. or less, and more preferably 460 ° C. or less.
- the heat treatment temperature does not reach the initial range, the carbonization of the foreign matter may not proceed sufficiently, and if the heat treatment temperature is above the predetermined range, the deterioration of the polyimide film proceeds and the Troubles such as breaking of the film during peeling are likely to occur.
- the heat treatment time After heating and reaching a predetermined temperature, it is held for 5 seconds or longer, preferably 30 seconds or longer, more preferably 100 seconds or longer, and then cooling is performed. If the holding time is extended more than necessary, the polyimide film tends to deteriorate.
- the rate of temperature increase heating is preferably performed at a rate of temperature increase of 5 ° C./min to 200 ° C./min. If the temperature is increased at a rate of 200 ° C./min or more, the number of blisters may increase.
- heat treatment is performed at a temperature of 350 ° C. or more and less than 600 ° C., and preferably, cooling is performed to at least 200 ° C. at a rate of 10 ° C./min or more and 90 ° C./min or less after the heat treatment. It is preferable to do.
- the cooling rate is preferably 15 ° C./min or more, more preferably 25 ° C./min.
- the upper limit of the cooling rate is preferably 80 ° C./min or less, more preferably 70 ° C./min or less, still more preferably 60 ° C./min or less.
- ⁇ Reduced viscosity of polyamic acid ( ⁇ sp / C)> A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube. (When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved using N, N-dimethylacetamide and measured.)
- Thickness unevenness 100 ⁇ (maximum value ⁇ minimum value) / arithmetic mean value [%]
- the thickness of the polyimide film which is a 2nd polyimide film is measured with a stylus-type film thickness meter.
- the polyimide film and film thickness unevenness after peeling, and the film thickness and film thickness unevenness of the polyimide film before lamination were substantially in agreement.
- thermobalance measurement The temperature at which the mass of the sample decreased by 5% was defined as the thermal decomposition temperature. did.
- ⁇ Number of blister defects The number of blisters that can be confirmed with the naked eye was counted.
- the size of the blister that can be detected is 50 ⁇ m or more in average diameter.
- ⁇ Measurement of blister defect height The height of the blister part (convex defect) of the laminate of the polyimide film and the inorganic substrate was measured by a height measuring function using a Keyence color 3D laser microscope VK9710.
- ⁇ Thickness of silane coupling agent layer> The thickness was measured by an electron micrograph of the cross section of the laminate of the polyimide film and the inorganic substrate.
- polyimide precursor (polyamic acid) solution PV3 The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 545 parts by mass of pyromellitic anhydride and 500 parts by mass of 4,4′diaminodiphenyl ether were 8000 parts by mass of N, N-dimethylacetamide.
- the polyamic acid solution [PV3] was obtained by reacting in the same manner while keeping the temperature at 20 ° C. or lower.
- the polyamic acid solution [PV1] obtained in the production example was defoamed and then applied to the smooth surface of a polyester film A4100 manufactured by Toyobo Co., Ltd. using a comma coater, and the drying temperature was 95 ° C. with a continuous dryer.
- the polyamic acid film was dried for 5 minutes at 110 ° C. for 10 minutes.
- the obtained polyamic acid film is peeled off from the polyester film, and both ends of the film are held with pins, and heat-treated at 250 ° C. for 3 minutes and at 485 ° C. for 3 minutes in a continuous heat treatment furnace, to room temperature.
- the polyimide film [PF1a] was obtained by cooling.
- Table 1 shows the evaluation results of the obtained polyimide film. “Film deposition” in the table indicates that the polyimide film obtained by this method was used. Similarly, the polyimide film shown in Table 1 was obtained by performing solution film formation in the same manner except that the polyamic acid solution, film formation method, coating film thickness, drying, and heat treatment conditions were changed. The results are shown in Table 1.
- ⁇ Inorganic substrate (support)> A glass plate for liquid crystal display having a thickness of 370 mm ⁇ 470 mm and a thickness of 0.7 mm was used as the substrate [G1].
- UV / ozone treatment Using a UV / ozone cleaning reformer manufactured by Lan Technical Service, the inorganic substrate was subjected to UV / ozone treatment for 1 minute with a distance between the lamp and the inorganic substrate of 30 mm.
- ⁇ Film cleaning treatment> The obtained polyimide film was washed using a continuous wet film washing apparatus, and further dried and held for 5 minutes in clean dry air at 120 ° C. for re-drying.
- the cleaning liquid used in the wet cleaning apparatus is purified by membrane filtration until the specific resistance is 15 M ⁇ ⁇ cm or more, and then aerated from ozone-containing clean air 2 generated by an ozonizer, resulting in an ozone concentration of 10 ppm or more. It was adjusted as follows.
- ⁇ Plasma treatment> ⁇ Plasma treatment of film>
- the polyimide film was cut into a size 10 mm smaller than the long side and the short side of the glass substrate, and processed with a single wafer vacuum plasma apparatus.
- As the vacuum plasma processing RIE mode using parallel plate type electrodes and RF plasma processing are adopted, nitrogen gas is introduced into the vacuum chamber, high frequency power of 13.54 MHz is introduced, and the processing time is 3 minutes.
- a gas barrier layer was formed by the following method using a general plasma CVD apparatus.
- Silane gas (SiH4), ammonia gas (NH3), nitrogen gas (N2), and hydrogen gas (H2) were used as source gases.
- the supply amounts of various gases were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas, and the film forming pressure was 60 Pa.
- the plasma to be supplied was 3000 W at 13.58 MHz.
- a bias power of 500 W was supplied to a glass plate (substrate holder) at a frequency of 400 kHz.
- Example 1 After the polyimide film [PF1a] to be a polyimide film is subjected to plasma treatment, the polyimide film is overlaid on the silane coupling agent-treated surface of the inorganic substrate that has been treated with the silane coupling agent, and temporarily bonded with a roll laminator Then, the substrate was placed in a clean bench and placed on a hot plate adjusted to 150 ° C. so that the inorganic substrate side was in contact with the hot plate, and heat treatment was performed for 3 minutes to obtain a laminate of a polyimide film and an inorganic substrate. The obtained laminate of polyimide film and inorganic substrate was stored for 12 hours or more in an environment of a temperature of 20 to 25 ° C. and a relative humidity of 65 ⁇ 30%.
- the obtained laminate of polyimide film and inorganic substrate was heat-treated in a 450 ° C. inert oven for 30 minutes. It was taken out from the oven, placed on a separately prepared copper plate adjusted to a predetermined temperature between 25 ° C. and 180 ° C. so that the inorganic substrate (glass plate) side was in contact, and rapidly cooled to a temperature of 200 ° C. or less.
- the cooling rate was controlled by the temperature of the copper plate.
- the average cooling rate required when cooling from 450 ° C. to 200 ° C. was defined as the cooling rate.
- the number of blisters present in the laminate of the obtained polyimide film and inorganic substrate was counted and classified according to size. Further, the number density was determined by dividing the total number of blisters by the laminate area. Furthermore, the height of all the blisters was measured with a laser microscope, the average value was determined, and the product of the average height of blisters and the number density was determined. Arbitrary five blisters counted were selected, the polyimide film side was cut open, and the contained foreign particles were analyzed. As a result, it was confirmed that all were carbide particles. The results are shown in Table 2. In Tables 2, 3, and 4, inert represents treatment in an atmosphere substituted with nitrogen. The size 50 ⁇ m-1 mm means 50 ⁇ m or more and less than 1 mm, the size 1-2 mm means 1 mm or more and less than 2 mm, and the size 2-3 mm means 2 mm or more and 3 mm or less.
- Example 2 to 9 Comparative Examples 1 to 6>
- Table 4 show the height distribution of blisters present in each laminate.
- 5 blisters were selected for each laminate, and the inclusions of the blisters were analyzed to confirm that the inclusions were carbide particles.
- N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine) is formed on ITO with a thickness of 30 nm, and 1,3-bis (N-carbazolyl) benzene is formed thereon. It was formed to a thickness of 10 nm.
- the following compound 1 and 4,4′-bis (N-carbazolyl) -1,1′-biphenyl were co-evaporated from different vapor deposition sources to form a 20 nm thick layer as a light emitting layer. At this time, the concentration of Compound 1 was 10% by weight.
- 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene was formed to a thickness of 40 nm, and lithium fluoride was vacuum-deposited on it to a thickness of 0.8 nm.
- ITO was formed in the same manner as a cathode.
- a gas barrier layer was further formed thereon.
- a flexible organic EL element was produced by peeling off the glass plate.
- the quality of the light-emitting element was visually determined for the obtained organic EL element, and the case where the number of black spots (non-light-emitting point) was 1 or less in terms of a square of 10 cm on a side was ⁇ , and the case where it was 3 or less was rated 4 The case of more than one was marked with x.
- Table 2, Table 3, and Table 4. As is apparent from the results, it was shown that a good device can be produced by using the laminate of the polyimide and the inorganic substrate of the present invention.
- the laminate of the present invention can be suitably used as a substrate for producing a flexible electronic device such as a flexible display element.
- the present invention can be widely applied to various flexible electronic devices, MEMS elements, sensor elements, solar cells, wearable elements, and the like.
- Inorganic substrate 2 Polyimide film 3: Foreign matter (carbide particles) h: Blister height (convex defect height) w: Blister size (blister diameter)
Abstract
Description
かかる手段により得られる高分子フィルムは、脆く裂けやすいため、高分子フィルム表面に形成された機能素子は支持体から剥離する際に破壊してしまう場合が多い。特に支持体から大面積のフィルムを剥離するのは極めて難しく、およそ工業的に成り立つ収率を得ることはできない。このような事情に鑑み、機能素子を形成するための高分子フィルムと支持体との積層体として、耐熱性に優れ強靭で薄膜化が可能なポリイミドフィルムを、シランカップリング剤を介して無機物からなる支持体(無機層)に貼り合わせてなる積層体が提案されている(特許文献4~5)。
高分子フィルムと無機基板を比較的厚い接着剤層を介して貼り合わせる場合には、異物が接着材層に埋没してしまうために、比較的ブリスターは生じにくい。しかしながら、接着材層が薄い場合、特に異物の高さが接着材層よりも大なる場合にはブリスターが発生してしまう。
[1] ポリイミドフィルムと無機基板の積層体において、少なくとも(a)または(b)の条件を満たすことを特徴とするポリイミドフィルムと無機基板の積層体。
(a)ブリスター欠点の個数密度50個/平方メートル以下であり、ブリスターの平均高さが2μm以下であり、ブリスター個数密度(個/平方メートル)とブリスターの平均高さ(μm)との積が20以下であること。
(b)ポリイミドフィルムと無機基板の積層体において、高さ3μm以上のブリスター個数が10個/平方mであること。
[2] 面積が0.157平方メートル以上であることを特徴とする[1]記載のポリイミドフィルムと無機基板の積層体。
[3] 前記ブリスターが、内部に炭化物粒子を内包する事を特徴とする[1]または[2]に記載のポリイミドフィルムと無機基板の積層体。
[4] 前記ポリイミドフィルムと無機基板の間に、厚さ5nm~500nmのシランカップリング剤縮合物層が存在する事を特徴とする[1]から[3]のいずれかに記載のポリイミドフィルムと無機基板の積層体。
[5] ポリイミドフィルムと無機基板を積層体した後、350℃以上600℃未満の温度で熱処理することを特徴とする[1]から[4]のいずれかに記載のポリイミドフィルムと無機基板の積層体の製造方法。
[6] ポリイミドフィルムと無機基板を積層体した後、350℃以上600℃未満の温度で熱処理し、 熱処理後に10℃/分以上、90℃/分以下の速度で少なくとも200℃まで冷却することを特徴とする[5]に記載のポリイミドフィルムと無機基板の積層体の製造方法。
[7] ポリイミドと無機基板を積層する前工程として、あらかじめオゾンにて処理された超純水にてポリイミドフィルムを洗浄することを特徴とする請求項5または6に記載のポリイミドフィルムと無機基板の積層体の製造方法。
[8] 前記冷却時に、ポリイミドフィルムと無機基板の積層体の無機基板側を、温度が180℃以下の金属板に接触させることにより冷却することを特徴とする[5]から[7]のいずれかに記載のポリイミドフィルムと無機基板の積層体の製造方法。
しかしながら、粘着剤や環境由来の有機異物、生体由来の異物などは比較的柔軟であり、場合によっては粘着性を有するため単純な洗浄処理で完全に除去することは難しい。一方で、そのような柔軟性、粘着性を有する有機物は、本発明で用いるポリイミドフィルムおよび無機基板に比較し耐熱性に劣り、高温前処理にて熱分解させることによる除去ができると考えられる。
しかしながら実際の行程でそのような前処理行程を設ける事は加熱から冷却による製造時間の延長、ならびに、新たな異物付着ないしハンドリングに伴うキズの生成などのリスクが高く非現実的である。
サイズの大きな基板では加熱速度、冷却速度に斑が生じやすい。本発明では特に冷却速度の斑を小さくすることが肝要である。したがって本発明では冷却時に積層体を高比熱の物質、例えば金属板などに直接接触させることにより冷却することが好ましい。
オゾン処理は、例えばオゾナイザー等にて生成させた含オゾンクリーンエアに洗浄水を曝気する事により行うことができる。本発明では洗浄水中のオゾン濃度が3ppm以上、好ましくは6ppm以上、なお好ましくは9ppm以上、さらに好ましくは20ppm以上とする事が好ましい。オゾン濃度の上限は特に制限されないが、概ね200ppm程度である。
脂環式テトラカルボン酸類は、透明性を重視する場合には、例えば、全テトラカルボン酸類の80質量%以上が好ましく、より好ましくは90質量%以上、さらに好ましくは95質量%以上である。
本発明における脂環式ジアミン類としては、例えば、1,4-ジアミノシクロヘキサン、4,4’-メチレンビス(2,6-ジメチルシクロヘキシルアミン)等が挙げられる。
(a)芳香族テトラカルボン酸二無水物と、少なくともベンゾオキサゾール骨格を有するジアミンを含むジアミンとの縮合物のフィルム、
(b)芳香族テトラカルボン酸二無水物と、少なくとも分子内にエーテル結合を有するジアミンを含むジアミンとの縮合物のフィルム、
(c)芳香族テトラカルボン酸二無水物と、少なくともフェニレンジアミンを含むジアミンとの縮合物のフィルム、
(d)ビフェニルテトラカルボン酸二無水物と、芳香族ジアミンとの縮合物のフィルム、
から選択される少なくとも一種のポリイミドフィルムからなることが好ましい。
本発明におけるシランカップリング剤は、無機板とポリイミドフィルムとの間に物理的ないし化学的に介在し、両者間の接着力を高める作用を有する化合物を云う。
シランカップリング剤の好ましい具体例としては、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、2-(3,4-エポキシシクロへキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-(ビニルベンジル)-2-アミノエチル-3-アミノプロピルトリメトキシシラン塩酸塩、3-ウレイドプロピルトリエトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアネートプロピルトリエトキシシラン、トリス-(3-トリメトキシシリルプロピル)イソシアヌレート、クロロメチルフェネチルトリメトキシシラン、クロロメチルトリメトキシシラン、アミノフェニルトリメトキシシラン、アミノフェネチルトリメトキシシラン、アミノフェニルアミノメチルフェネチルトリメトキシシラン、ヘキサメチルジシラザンなどが挙げられる。
本発明では、特に好ましいシランカップリング剤としては、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、2-(3,4-エポキシシクロへキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、アミノフェニルトリメトキシシラン、アミノフェネチルトリメトキシシラン、アミノフェニルアミノメチルフェネチルトリメトキシシランなどが挙げられる。プロセスで特に高い耐熱性が要求される場合、Siとアミノ基の間を芳香族基でつないだものが望ましい。
なお本発明では必要に応じて、リン系カップリング剤、チタネート系カップリング剤等を併用しても良い。
本発明ではこのシランカップリング剤塗布方法として、好ましくは気相を介する気相塗布法を用いる事ができる。気相塗布法とは、気化させたシランカップリング剤に無機基板を暴露することにより塗布を行う。シランカップリング剤塗布をシランカップリング剤処理と言い換えても良い。気化とはシランカップリング剤の蒸気、すなわち実質的に気体状態のシランカップリング剤あるいは、微粒子状態のシランカップリング剤が存在する状態を指す。暴露とは、前記の気化したはシランカップリング剤を含んだ気体あるいは真空状態に有機系高分子フィルムが接触していることを言う。
一方、生産効率向上および生産設備価格低減の観点からは、真空を使わない環境でのシランカップリング剤塗布が望ましい。例えば、チャンバー内に常圧下にて有機系高分子フィルムをセットし、チャンバー内を気化したシランカップリング剤を含む概ね常圧のキャリアガスを満たしてシランカップリング剤を堆積してから、再び気化したシランカップリング剤の無い状態に戻すまで、概略大気圧のままで行うことができる。
本発明のブリスターは肉眼で確認できる大きさの物を言う。より具体的には平面方向に観察したブリスターを円とした場合に直径が50μm以上のものを云う。なおここに直径はブリスターが歪んでいる場合には長径と短径の平均値である。
本発明ではさらに高さが2.2μm以上のブリスターの個数が、1平方mあたり10個以下であることが好ましく、7個以下である事がさらに好ましく、4個以下である事がさらに好ましく、2個以下である事がさらに好ましく。0個であることがなお好ましい。
本発明ではさらに高さが1.4μm以上のブリスターの個数が、1平方mあたり10個以下であることが好ましく、7個以下である事がさらに好ましく、4個以下である事がさらに好ましく、2個以下である事がさらに好ましく。0個であることがなお好ましい。
本発明ではさらに高さが0.8μm以上のブリスターの個数が、1平方mあたり10個以下であることが好ましく、7個以下である事がさらに好ましく、4個以下である事がさらに好ましく、2個以下である事がさらに好ましく。0個であることがなお好ましい。
本発明におけるブリスター総数の個数密度は50個/平方メートル以下である事が好ましい。
無機基板としてガラス板を用いた場合には、ガラス板側からの観察により内包される異物(粒子)の色を容易に識別できる。不透明な無機基板の場合には、フィルム側を切開して観察することができる。
熱処理の時間については加熱して所定温度に到達後に5秒以上保持、好ましくは30秒以上保持、さらに好ましくは100秒以上保持したのちに冷却すれば良い。必要以上に保持時間を延ばすと、ポリイミドフィルムの劣化が生じやすくなる。
昇温速度については、好ましくは5℃/分~200℃/分の昇温速度で加熱すれば良い。なお200℃/分以上の速度で昇温すると、ブリスターの個数が増加する場合がある。
ポリマー濃度が0.2g/dlとなるようにN-メチル-2-ピロリドン(又は、N,N-ジメチルアセトアミド)に溶解した溶液をウベローデ型の粘度管により30℃で測定した。(ポリアミド酸溶液の調製に使用した溶媒がN,N-ジメチルアセトアミドの場合は、N,N-ジメチルアセトアミドを使用してポリマーを溶解し、測定した。)
ポリイミドフィルムについては、積層体断面のSEM断面観察により求めた。なお、特に断りの無い限り、各ポリイミドフィルムの端部から1mm以上内側の領域において、無作為に選択した5点の膜厚の平均値をポリイミドフィルムの膜厚とした。
第2のポリイミドフィルムにおいては、ラミネート前のポリイミドフィルムないしは第2のポリイミドフィルムを積層体から90度剥離した後のフィルムの無作為に選択した10点の算術平均値を求め、膜厚とした。また、任意の10点の膜厚の最大値、最小値、算術平均値から、以下の式により膜厚斑[%]を算出した。
膜厚斑=100×(最大値-最小値)/算術平均値 [%]
なお第2のポリイミドフィルムであるポリイミドフィルムの厚さは触針式膜厚計で測定される。
また、良好に剥離できた場合には、剥離後のポリイミドフィルム、膜厚斑と、ラミネート前のポリイミドフィルムの膜厚および膜厚斑はほぼ一致した。
積層板から剥離したポリイミドフィルム(ポリイミドフィルム)を試料とし、150℃にて30分間乾燥した後に、下記条件で熱天秤測定(TGA)を行い、試料の質量が5%減る温度を熱分解温度とした。
装置名 : MACサイエンス社製TG-DTA2000S
パン : アルミパン(非気密型)
試料質量 : 10mg
昇温開始温度 : 30℃
昇温速度 : 20℃/min
雰囲気 : アルゴン
ポリイミドフィルム(フィルム)として得られた試料において、下記条件にて伸縮率を測定し、30℃~45℃、45℃~60℃、…と15℃の間隔での伸縮率/温度を測定し、この測定を300℃まで行い、全測定値の平均値をCTEとして算出した。
機器名 : MACサイエンス社製TMA4000S
試料長さ : 20mm
試料幅 : 2mm
昇温開始温度 : 25℃
昇温終了温度 : 400℃
昇温速度 : 5℃/min
雰囲気 : アルゴン
肉眼にて確認できるブリスター個数を計数した。検知できるブリスターのサイズは平均径で50μm以上である。
<ブリスター欠点の高さ測定>
ポリイミドフィルムと無機基板の積層体のブリスター部分(凸欠点)の高さは、キーエンス製カラー3Dレーザー顕微鏡VK9710による高さ測定機能により計測した。
ポリイミドフィルムと無機基板の積層体の断面の電子顕微鏡写真により厚さを計測した。
内部に異物を含むブリスター部分の、ポリイミドフィルムを切開し、異物の顕微IR測定を行い、得られたIRスペクトルの吸収が全体的に緩やかで幅広く、1000-3500cm-1の領域で樹脂由来の特徴的な吸収が確認できないことをもってして、炭化物である事を確認した。
[ポリイミド前駆体(ポリアミド酸)溶液PV1の製造]
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール223質量部、N,N-ジメチルアセトアミド4416質量部を加えて完全に溶解させた後、ピロメリット酸二無水物217質量部、25℃の反応温度で24時間攪拌すると、褐色で粘調なポリアミド酸溶液[PV1」を得た。
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、テトラカルボン酸二無水物として3,3',4,4'-ビフェニルテトラカルボン酸二無水物398質量部、パラフェニレンジアミン132質量部、4,4'ジアミノジフェニルエーテル30質量部を4600質量部のN、N-ジメチルアセトアミドに溶解し、25℃の反応温度で24時間攪拌すると、褐色で粘調なポリアミド酸溶液[PV2]を得た。
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、ピロメリット酸無水物545質量部、4,4'ジアミノジフェニルエーテル500質量部を8000質量部のN、N-ジメチルアセトアミドに溶解し、温度を20℃以下に保ちながら同様に反応させてポリアミド酸溶液[PV3]を得た。
[ポリイミド前駆体(ポリアミド酸)溶液PV4の製造]
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、ピロメリット酸二無水物545質量部、パラフェニレンジアミン153質量部、4,4'ジアミノジフェニルエーテル200質量部を8000質量部のN、N-ジメチルアセトアミドに溶解し、温度を20℃以下に保ちながら同様に反応させてポリアミド酸溶液[PV4]を得た。
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、反応容器に窒素雰囲気下、2,2’-ジメチル-4,4’-ジアミノビフェニル155.9質量部とN,N-ジメチルアセトアミド1200質量部を仕込んで溶解させた後、反応容器を冷却しながらシクロブタンテトラカルボン酸二無水物142.9質量部を固体のまま分割添加し、室温で5時間攪拌した。その後N,N-ジメチルアセトアミド1000質量部で希釈し、還元粘度4.20dl/gのポリアミド酸溶液[PV5]を得た。
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、反応容器に窒素雰囲気下、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル176.5質量部とN,N-ジメチルアセトアミド1200質量部を仕込んで溶解させた後、反応容器を冷却しながら1,2,4,5-シクロヘキサンテトラカルボン酸二無水物122.9質量部を固体のまま分割添加し、室温で18時間攪拌した。その後N,N-ジメチルアセトアミド500質量部で希釈し、還元粘度3.26dl/gのポリアミド酸溶液[PV6]を得た。
窒素導入管,温度計,攪拌棒を備えた反応容器内を窒素置換した後、テトラカルボン酸二無水物として3,3',4,4'-ビフェニルテトラカルボン酸二無水物398質量部、パラフェニレンジアミン148質量部、4600質量部のN、N-ジメチルアセトアミドに溶解し、25℃の反応温度で24時間攪拌すると、褐色で粘調なポリアミド酸溶液[PV7]を得た。
製造例にて得られたポリアミド酸溶液[PV1]を脱泡後にコンマコーターを用いて、東洋紡株式会社製ポリエステルフィルムA4100の平滑面に塗布し、連続式乾燥機にて乾燥温度を95℃にて5分、110℃にて10分間乾燥しポリアミド酸フィルムとした。次いで得られたポリアミド酸フィルムをポリエステルフィルムから剥離し、フィルムの両端をピンにて把持し、連続式の熱処理炉にて250℃にて3分、485℃にて3分間熱処理を行ない、室温まで冷却してポリイミドフィルム[PF1a]を得た。得られたポリイミドフィルムの評価結果を表1に示す。表中の「フィルム成膜」はこの方法によって得られたポリイミドフィルムを用いた事を示す。
以下同様にポリアミド酸溶液、成膜方法、塗布膜厚、乾燥、熱処理条件,を代えて溶液成膜を行い表1に示すポリイミドフィルムを得た。結果を表1に示す。
基板[G1]として370mm×470mm、厚さ0.7mmの液晶ディスプレイ用ガラス板を用いた。
基板[G2]として550mm×650mm、厚さ0.7mmの液晶ディスプレイ用ガラス板を用いた。
ランテクニカルサービス社製UV/オゾン洗浄改質装置を用い、ランプと無機基板との距離を30mmとして無機基板に1分間のUV/オゾン処理を行った。
ホットプレートと無機基板の支持台とを備えたチャンバーをクリーンな乾燥窒素で置換した後、UV/オゾン処理を行った無機基板を支持台に設置し、無機基板の200mm下方に液面が位置するようにシランカップリング剤(3-アミノプロピルトリメトキシシラン)を満たしたシャーレを置き、シャーレをホットプレートにて100℃に加熱し、無機基板の下面をシランカップリング剤蒸気に3分間暴露した後にチャンバーから取り出し、クリーンベンチ内に設置し、120℃に調温されたホットプレートに無機基板の暴露面とは逆側を熱板に接するように乗せ、1分間の熱処理を行い、シランカップリング剤処理とした。
得られたポリイミドフィルムを、連続式の湿式フィルム洗浄装置を用いて洗浄し、さらに搬送しつつ120℃のクリーンドライエア中にて5分間保持して再乾燥を行った。なお湿式洗浄装置にて用いた洗浄液は、比抵抗が15MΩ・cm以上となるまで膜濾過により精製した後、オゾナイザーにて生成させた含オゾンクリーンエア2より曝気し、オゾン濃度が10ppm以上となるよう調整された。
<フィルムのプラズマ処理>
ポリイミドフィルムを、ガラス基板の長辺、短辺より各々10mm小さいサイズに裁断し、枚葉式の真空プラズマ装置により処理を行った。真空プラズマ処理としては、平行平板型の電極を使ったRIEモード、RFプラズマによる処理を採用し、真空チャンバー内に窒素ガスを導入し、13.54MHzの高周波電力を導入するようにし、処理時間は3分間とした。
一般的なプラズマCVD装置を用いて、以下の手法によりガスバリア層を形成した。原料ガスとしてシランガス(SiH4),アンモニアガス(NH3),窒素ガス(N2),および水素ガス(H2)を用いた。各種ガスの供給量は、シランガスが100sccm、アンモニアガスが200sccm、窒素ガスが500sccm、水素ガスが500sccmとした成膜圧力は60Paとした。供給するプラズマは、13.58MHzで3000Wとした。成膜中は、ガラス板(基板ホルダ)に、周波数400kHzで500Wのバイアス電力を供給した。
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、
CBA:シクロブタンテトラカルボン酸二無水物、
CHA:1,2,4,5-シクロヘキサンテトラカルボン酸二無水物、
ODA:4,4'ジアミノジフェニルエーテル、
PDA:フェニレンジアミン、
DAMBO:5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、
BPA:2,2’-ジメチル-4,4’-ジアミノビフェニル、
FA:2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル、
CTE :線膨張係数、
ポリイミドフィルムとなるポリイミドフィルム[PF1a]に、プラズマ処理を行い、シランカップリング剤処理を行った無機基板のシランカップリング剤処理面に重なるようにポリイミドフィルムを重ね、ロールラミネータにて仮圧着した後、クリーンベンチ内に設置し、150℃に調温されたホットプレートに無機基板側を熱板に接するように乗せ、3分間熱処理を行い、ポリイミドフィルムと無機基板の積層体を得た。得られたポリイミドフィルムと無機基板の積層体を、温度20~25℃、相対湿度65±30%の環境下で12時間以上保管した。
以上の結果を表2に示す。なお表2、表3、表4においてイナートは窒素置換した雰囲気下での処理を示す。またサイズ50μm-1mmは、50μm以上1mm未満、サイズ1-2mmは1mm以上2mm未満、サイズ2-3mmは2mm以上3mm以下を意味する。
以下、無機基板、ポリイミドフィルム、各々の処理条件、等を適宜替えて実験を行い表2,表3.表4、に示す実施例2~実施例9、比較例1~6のポリイミドと無機基板の積層体を得た。各々の積層体に存在するブリスターの高さ分布を表2、表3、表4に示す。なお、実施例1と同様に各積層体毎に任意のブリスター5点を選択し、ブリスターの内包物の分析を行いいずれも内包物が炭化物粒子である事を確認した。
実施例1~9、比較例1~6にて得られたポリイミドと無機基板との積層体を100℃で1時間乾燥させたのち、ガスバリア層を形成する真空装置にセットし減圧した。所定の真空度に達したことを確認した後にポリイミドフィルムの表面に、ガスバリア層として窒化珪素薄膜を形成した。次いで、積相体のガスバリア層の表面に、10-5Paオーダーの真空度にて各薄膜を蒸着して積層した。先ず成膜温度400℃にて、膜厚100nmのインジウム・スズ酸化物(ITO)からなる陽極を形成した。その後、ITO上にN,N'-ジ(1-ナフチル)-N,N'-ジフェニルベンジジン)を30nmの厚さに形成し、この上に、1,3-ビス(N-カルバゾリル)ベンゼンを10nmの厚さに形成した。次に、下記の化合物1と4,4'-ビス(N-カルバゾリル)-1,1'-ビフェニルを異なる蒸着源から共蒸着し、20nmの厚さの層を形成して発光層とした。この時、化合物1の濃度は10重量%とした。次に、1,3,5-トリス(1-フェニル-1H-ベンズイミダゾール-2-イル)ベンゼンを40nmの厚さに形成し、この上にフッ化リチウムを0.8nm真空蒸着した。さらに、同様にITOを形成し陰極とした。その上からさらにガスバリア層を形成した。最後にガラス板から剥がすことで、フレキシブルな有機EL素子を作製した。
得られた有機EL素子について発光素子の品位を目視判定し、一辺が10cmの正方形換算にて黒点(無発光点)が1個以下である場合を◎、3個以下である場合を○、4個以上である場合を×とした。
結果を表2、表3、表4に示す。
結果から明らかなように、本発明のポリイミドと無機基板の積層体を使うと、良好なデバイスを作製することができることが示された。
2:ポリイミドフィルム
3:異物(炭化物粒子)
h:ブリスター高さ(凸欠点高さ)
w:ブリスターサイズ(ブリスター径)
Claims (7)
- ポリイミドフィルムと無機基板の積層体において、少なくとも(a)または(b)の条件を満たすことを特徴とするポリイミドフィルムと無機基板の積層体。
(a)ブリスター欠点の個数密度50個/平方メートル以下であり、ブリスターの平均高さが2μm以下であり、ブリスター個数密度(個/平方メートル)とブリスターの平均高さ(μm)との積が20以下であること。
(b)ポリイミドフィルムと無機基板の積層体において、高さ3μm以上のブリスター個数が10個/平方mであること。 - 面積が0.157平方メートル以上であることを特徴とする請求項1記載のポリイミドフィルムと無機基板の積層体。
- 前記ブリスターが、内部に炭化物粒子を内包する事を特徴とする請求項1または請求項2に記載のポリイミドフィルムと無機基板の積層体。
- 前記ポリイミドフィルムと無機基板の間に、厚さ5nm~500nmのシランカップリング剤縮合物層が存在する事を特徴とする請求項1から請求項3のいずれかに記載のポリイミドフィルムと無機基板の積層体。
- ポリイミドフィルムと無機基板を積層体した後、350℃以上600℃未満の温度で熱処理することを特徴とする請求項1から請求項4のいずれかに記載のポリイミドフィルムと無機基板の積層体の製造方法。
- ポリイミドフィルムと無機基板を積層体した後、350℃以上600℃未満の温度で熱処理し、 熱処理後に10℃/分以上、90℃/分以下の速度で少なくとも200℃まで冷却することを特徴とする請求項5に記載のポリイミドフィルムと無機基板の積層体の製造方法。
- ポリイミドと無機基板を積層する前工程として、あらかじめオゾンにて処理された超純水にてポリイミドフィルムを洗浄することを特徴とする請求項5または6に記載のポリイミドフィルムと無機基板の積層体の製造方法。
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